WO2015014791A1 - Benzimidazolo[2,1-b][1,3]benzothiazoles for electronic applications - Google Patents

Benzimidazolo[2,1-b][1,3]benzothiazoles for electronic applications Download PDF

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Publication number
WO2015014791A1
WO2015014791A1 PCT/EP2014/066174 EP2014066174W WO2015014791A1 WO 2015014791 A1 WO2015014791 A1 WO 2015014791A1 EP 2014066174 W EP2014066174 W EP 2014066174W WO 2015014791 A1 WO2015014791 A1 WO 2015014791A1
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Prior art keywords
group
substituted
formula
optionally
cisalkyl
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PCT/EP2014/066174
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French (fr)
Inventor
Thomas Schäfer
Peter Murer
Ute HEINEMEYER
Julia KOHLSTEDT
Heinz Wolleb
Annemarie Wolleb
Soichi Watanabe
Hideaki Nagashima
Toshio Sakai
Christian Lennartz
Gerhard Wagenblast
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Basf Se
Idemitsu Kosan Co., Ltd.
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Application filed by Basf Se, Idemitsu Kosan Co., Ltd. filed Critical Basf Se
Publication of WO2015014791A1 publication Critical patent/WO2015014791A1/en
Priority to EP15747561.7A priority Critical patent/EP3174885B1/en
Priority to PCT/IB2015/055667 priority patent/WO2016016791A1/en

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to compounds of formula I, a process for their production and their use in electronic devices, especially electroluminescent devices.
  • the compounds of formula I may provide improved efficiency, stability, manufacturability and/or spectral characteristics of electroluminescent devices.
  • WO2012139692 relates to electronic devices which comprise an anode, a cathode and at least one organic layer, where the organic layer comprises one or more substituted ben
  • Y can be S and n can be 0 or 1 , Z is
  • R 1 can be an aromatic or hetero aromatic ring system.
  • DE102012000064 describes compounds of formula (1 ) and their use in organic light emitting devices (OLEDs). Among others X can be C. If X is C, n is 1.
  • WO20121 10182 describes compounds of formula (I),
  • X and Y can be S and Z is CR 2 , or N.
  • US20050074632 relates to compounds of formula (1 ), wherein
  • US20050079387 relates to compounds of formula Ai-A 2 -A 3 (1 ), wherein
  • X and X ' can be S, O, or Se.
  • the compounds of formula A1-A2-A3 CI ) are used as blue luminescent material or as hosts for phosphorescent, or fluorecent dopants.
  • US2790172 relates to compounds of formula , wherein R and R 1 are H, lower alkyl, lower alkoxy, or phenyl; or R 1 and R can form a 6 membered carbocylcle; and a process for their production.
  • EWG is an elecron withdrawing group, like CN, NO2, CI, F, or CF3 and R is NO2, or OMe.
  • WO201 1160757 relates to an electronic device comprising an anode, cathode and at least
  • WO2013/050401 describes 4H-imidazo[1 ,2-a]imidazoles of formula
  • WO2014/009317 relates to compounds of formula (I), a process for their production and their use in electronic devices, especially electroluminescent devices.
  • the compounds of formula I When used as host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency, stability, manufac- turability, or spectral characteristics of electrolumine
  • WO2014/044722 relates to compounds of formula (I), which are characterized in that they substituted by benzimidazo[1 ,2-a]benzimidazo-5-yl and/or benzimidazo[1 ,2-a]benzimidazo-2,5-ylene groups and in that at least one of the substitu- ents B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 and B 8 represents N; a process for their production and their use in electronic devices, especially electroluminescent devices.
  • the present invention provides further materials suitable for use in OLEDs and further applications in organ- ic electronics. More particularly, it should be possible to provide charge transport materials, charge/exciton blocker materials and matrix materials for use in OLEDs.
  • the materials should be suitable especially for OLEDs which comprise at least one phosphorescence emitter, especially at least one green emitter or at least one blue emitter.
  • the materials should be suitable for providing OLEDs which ensure good efficiencies, good operative lifetimes and a high stability to thermal stress, and a low use and operating voltage of the OLEDs.
  • benzimidazolo[2,1-b][1 ,3]benzothiazole derivatives are found to be suitable for use in organo-electroluminescent devices.
  • said derivatives are suitable charge transport materials, or host materials for phosphorescent emitters with good efficiency and durability.
  • hole transporters and bipo- lar hosts hole transporting units are required.
  • electron transporting units are required.
  • the benzimidazolo[1 ,2- ajbenzimidazole basic skeleton described in WO2011160757 represents a hole transporter unit, which is responsible for good hole transport and hole injection. It has surprisingly been found that the benzimidazolo[2,1-b][1 ,3]benzothiazole basic skeleton described in the pre- sent application represents an electron transporting unit, which is responsible for good electron transport and electron injection.
  • Y 1 and Y 2 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally be substituted by G;
  • R 1 and R 6 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a group of formula -(AV(A 2 )p-(A 3 ) q -(A 4 ) r R 16 ,
  • o 0, or 1
  • p is 0, or 1
  • q is 0, or 1
  • r is 0, or 1
  • a 1 , A 2 , A 3 and A 4 are independently of each other a C6-C2 4 arylen group, which can optionally be substituted by G, or a C2-C3oheteroarylen group, which can optionally be substituted by G;
  • R 16 is H, -NR 10 R 11 , or -Si(R 12 )(R 13 )(R 14 ), a C 6 -C 24 aryl group, which can optionally be substi- tuted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • R 10 and R 11 are independently of each other a C6-C2 4 aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • R 12 , R 13 and R 14 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D;
  • a C6-C2 4 aryl group which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • E is -OR 69 , -SR 69 , -NR 65 R
  • G is E, or a d-dsalkyl group, a C6-C2 4 aryl group, a C6-C2 4 aryl group, which is substituted by F, Ci-Ci8alkyl, or C-i-C-isalkyl, which is substituted by F and/or interrupted by O; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, Ci-Cisalkyl, - Si(R 2' )(R 3' )(R 14' ), or Ci-Ci 8 alkyl which is interrupted by O;
  • R14' a re independently of each other a d-dsalkyl group, which can optionally be interupted by O; a C6-Ci4arylgroup, which can optionally be substituted by d-dsalkyl ; or a C2-Cioheteroaryl group, which can optionally be substituted by d-dsalkyl ;
  • R 63 and R 64 are independently of each other H, d-dsaryl; d-dsaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-; R 65 and R 66 are independently of each other a C6-Cisaryl group; a d-dsaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; a Ci-Cisalkyl group; or a d-dsalkyl group, which is interrupted by -0-; or
  • R 65 and R 66 together form a five or six membered ring
  • R 67 is a Ce-Cisaryl group; a d-dsaryl group, which is substituted by d-dsalkyl, or Ci- dsalkoxy; a d-dsalkyl group; or a d-dsalkyl group, which is interrupted by -0-,
  • R 68 is H; a d-dsaryl group; a d-dsaryl group, which is substituted by d-dsalkyl, or Ci- dealkoxy; a d-dsalkyl group; or a d-dsalkyl group, which is interrupted by -0-,
  • R 69 is a C6-Ciearyl; a d-dsaryl, which is substituted by d-dsalkyl, or d-dsalkoxy; a d- dealkyl group; or a d-dsalkyl group, which is interrupted by -O-,
  • R 70 and R 71 are independently of each other a d-dsalkyl group, a d-dsaryl group, or a d-dsaryl group, which is substituted by d-dsalkyl, and
  • R 72 is a d-dsalkyl group, a d-dsaryl group, or a d-dsaryl group, which is substituted by d-dsalkyl, with the proviso that at least one of the substituents R 1 and R 6 represent a group of formula -(A ) 0 -(A 2 )p-(A 3 ) q -(A 4 ) r R 16 and with the further proviso that R 16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
  • T I is preferably a compound of formula
  • R 1 , R 2 , R 3 , R 4 , R5, Re, R 7 and R 8 are independently of each other H, a d-dsalkyl group, which can optionally be substituted by E and or interupted by D; a d-dsaralkyl group, which can optionally be substituted by G, or a group of formula— (A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 , o is 0, or 1 , p is 0, or 1 , q is 0, or 1 , r is 0, or 1 ,
  • a 1 , A 2 , A 3 and A 4 are independently of each other a d-d 4 arylen group, which can optionally be substituted by G, or a d-doheteroarylen group, which can optionally be substituted by G;
  • R 16 is H, -NR 10 R 11 , or -Si(R 12 )(R 13 )(R 14 ), a d-d 4 aryl group, which can optionally be substi- tuted by G; or a d-doheteroaryl group, which can optionally be substituted by G;
  • R 10 and R 11 are independently of each other a d-d 4 aryl group, which can optionally be substituted by G; or a d-doheteroaryl group, which can optionally be substituted by G;
  • R 12 , R 13 and R 14 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • E is -OR 69 , -SR 69 , -NR 65 R 66 , -COR 68 , -COOR 67 , -CONR 65 R 66 , -CN, or F,
  • G is E, or a Ci-Cisalkyl group, a C6-C2 4 aryl group, a C6-C2 4 aryl group, which is substituted by F, Ci-Ci8alkyl, or Ci-Cisalkyl which is substituted by F and/or interrupted by O; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, Ci-Cisalkyl, - Si(R 2' )(R 3' )(R 14' ), or Ci-Ci 8 alkyl which is interrupted by O;
  • RI 4 ' are independently of each other a d-dsalkyl group, which can optionally be interupted by O; a C6-Ci 4 arylgroup, which can optionally be substituted by C-i-C-isalkyl ; or a C2-Cioheteroaryl group, which can optionally be substituted by Ci-Cisalkyl ;
  • R 63 and R 64 are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; Ci-Cisalkyl; or C-i-C-isalkyl which is interrupted by -0-;
  • R 65 and R 66 are independently of each other a C6-Cisaryl group; a di-deary! which is substituted by Ci-Cisalkyl, or d-dsalkoxy; a Ci-Cisalkyl group; or a d-dsalkyl group, which is interrupted by -0-; or
  • R 65 and R 66 together form a five or six membered ring
  • R 67 is a Ce-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci- Ci8alkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-,
  • R 68 is H; a C6-Cisaryl group; a di-deary! group, which is substituted by Ci-Cisalkyl, or Ci- Ci8alkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-,
  • R 69 is a C6-Ciearyl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci- Ciealkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-,
  • R 70 and R 71 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a Ce-Cisaryl group, which is substituted by Ci-Cisalkyl, and
  • R 72 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a di-deary! group, which is substituted by Ci-Cisalkyl, with the proviso that at least one of the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent a group of formula -(A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 and with the further proviso that R 16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
  • Certain compounds of the present invention have high triplet energy and can show, when used as host in combination with phosphorescent emitters, excellent power efficiencies.
  • the compounds of the present invention may be used for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electrolumi- nescent devices, such as, for example, organic light-emitting diodes (OLEDs).
  • organic solar cells organic photovoltaics
  • switching elements such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electrolumi- nescent devices, such as, for example, organic light-emitting diodes (OLEDs).
  • a further subject of the present invention is directed to an electronic device, comprising a compound according to the present invention.
  • the electronic device is preferably an electroluminescent device.
  • the compounds of formula I can in principal be used in any layer of an EL device, but are preferably used as host, charge transport and/or charge/exciton blocking material. Particularly, the compounds of formula I are used as host material for green, especially blue light emitting phosphorescent emitters.
  • a further subject of the present invention is directed to a charge transport layer, comprising a compound of formula I according to the present invention.
  • a further subject of the present invention is directed to an emitting layer, comprising a com- pound of formula I according to the present invention.
  • a compound of formula I is preferably used as host material in combination with a phosphorescent emitter.
  • a further subject of the present invention is directed to a charge/exciton blocking layer, comprising a compound of formula I according to the present invention.
  • D is preferably -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR 65 -, wherein R 65 is Ci-Ci 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C6-Ci 4 aryl, such as phenyl, tolyl, naphthyl, or biphenylyl, or C2-C3oheteroaryl, such as, for example, benzimid-
  • E is preferably -OR 69 ; -SR 69 ; -NR 6 5R 6 5; -COR 68 ; -COOR 67 ; -CON RssRss; or -CN; wherein R 65 , R 67 , R 68 and R 69 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-Ci 4 aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.
  • Ci-Cisalkyl such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, oc
  • G is preferably -OR 69 ; -SR 69 ; -NR 65 R 65 ; a d-dsalkyl group, a C 6 -Ci 4 aryl group, a C 6 - Ci 4 aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2- doheteroaryl group, which is substituted by F, or d-C-isalkyl; or -Si(R 2' )(R 3' )(R 14' ); wherein R 65 , R 67 , R 68 and R 69 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C
  • R 1 , R 2 , R 3 and R 6 are independently of each other a group of formula— (A )o-(A 2 )p-(A 3 ) q -(A 4 )rR 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above;
  • Y 1 and Y 2 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substi- tuted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally be substituted by G, wherein D, E and G are as defined above.
  • R 1 , R 2 , R 3 and R 6 are independently of each other a group of formula—(A 1 ), (A 3 )q-(A 4 ) r R 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above, or below.
  • formula (I) compounds of formula
  • R 3 and R 6 are independently of each other a group of formula— (A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above; c is 0, or 1 ; d is 0, or 1 ; and
  • Y 1 and Y 2 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally rein D, E and G are as de-
  • R 3 and R 6 are independently of each other a group of formula— (A 1 ) 0 -(A 2 ) p -(A 3 ) q - (A 4 )rR 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above, or below.
  • a 1 , A 2 , A 3 and A 4 are independently of each other a C6-C2 4 arylen group, which can optionally be substituted by G, or a C2-C3oheteroarylen group, which can optionally be substituted by G.
  • the C6-C2 4 arylen groups A 1 , A 2 , A 3 and A 4 which optionally can be substituted by G, are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1- naphthylene, or 2-naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9- fluorenylene, phenanthrylene, or anthrylene, which may be unsubstituted or substituted.
  • the C2-C3oheteroarylen groups A 1 , A 2 , A 3 and A 4 which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated-electrons such as, for example, benzofu- idylene
  • zothiophenylene phenoxythienylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazi- nylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinolylene, isochinolylene, phthalazinylene, naphthyridinylene, chinoxalinylene, chinazoli- nylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, iso- thiazolylene, phenothiazoly
  • C6-C24arylen groups are 1 ,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted, especially by C6-Cioaryl, C6-Cioaryl which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl.
  • Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, especially benzofuro[2,3-b]pyridylene, benzothiopheno[2,3-b]pyridylene , pyrido[2,3-b]indolylene , benzofuro[2,3-c]pyridylene, benzothiopheno[2,3-c]pyridylene , pyrido[2,3-c]indolylene fu- ro[3,2-b:4,5-b']dipyridylene, thieno[3,2-b:4,5-b']dipyridylene, pyrrolo[3,2-b:4,5- b']dipyridylene, dibenzofuranylene, dibenzothiophenylene , carbazolylene and benzimid- azo[1 ,2-a]benzimidazo-2,5-ylene , which can be un
  • the C6-C2 4 arylen and C2-C3oheteroarylen groups may be substituted by G.
  • G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3, a C6-Ci 4 aryl group, a C6-Ci 4 aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2-Cioheteroaryl group, which is substituted by F, or Ci-Cisalkyl.
  • Ci-Cisalkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3,
  • Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Cioheteroaryl group.
  • Phenyl, 1-naphthyl and 2- naphthyl are examples of a C6-Ci 4 aryl group.
  • a 1 , A 2 , A 3 and A 4 are independently of each other a group of the formula
  • X is O, S, or NR24
  • R 24 is a C6-C2 4 aryl group, which can optionally be substituted by G, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined above.
  • R 16 may be a C6-C2 4 aryl group, which can optionally be substituted by G, or a C2- C3oheteroaryl group, which can optionally be substituted by G.
  • the C6-C2 4 aryl group which optionally can be substituted by G, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted.
  • the C2-C3oheteroaryl group R 16 which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated ⁇ -electrons such as 9H-pyrido[2,3-b]indolyl, benzofuro[2,3- bjpyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyrrolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipy
  • the C6-C2 4 aryl and C2-C3oheteroaryl groups may be substituted by G.
  • G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl; -CF3, a C6-C-i 4 aryl group, a C6-Ci 4 aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2-Cioheteroaryl group, which is substituted by F, or Ci-Cisalkyl.
  • Prefered C2-C3oheteroaryl groups are pyridyl, triazinyl, pyrimidinyl, especially 9H-pyrido[2,3- b]indolyl, benzofuro[2,3-b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyr- rolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, benzimi azo-5-yl
  • azolo[2,1-b][1 ,3]benzothiazolyl ( , or ), carbazolyl, dibenzofuranyl, and dibenzothiophenyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C 4 alkyl; or C2-Ci 4 heteroaryl.
  • R 16 is preferably H, or a group of the formula -Si(R 12 )(R 13 )(R 14 ),
  • R 12 , R 13 and R 14 are independently of each other a phenyl group, which can optionally be substituted by one, or more Ci-Cisalkyl groups;
  • R 21 and R 21 ' are independently of each other H, a phenyl group, or a Ci-Cisalkyl group;
  • X is O, S, or NR 24 ,
  • R 24 is a C6-C2 4 aryl group, which can optionally be substituted by G, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined above.
  • o 0, or 1
  • p is 0, or 1
  • q is 0, or 1
  • r is 0, or 1
  • a 1 , A 2 , A 3 and A 4 are independently of each oth
  • the group of the formula -(A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 is a
  • the group of the formula -(A 1 ) 0 -(A 2 )p-(A 3 ) q -(A 4 ) r R 16 is a group of formula (Xlla), (Xllb), (Xllc), (Xllt), (Xlllb), (Xlllh), (Xllli), (Xlllj), (XlVb), (XIVc), (XIVo), (XIVp), (XlVq), (XIVo), (XIVp), (XlVq), (XIVz), (XVc), (XVd), (XVh), (XVI), (XVo), (XVq), (XVIc), (XVIe), (XVIf); (XVIIa), (XVIIe), (XVIIf), or (XVIIs).
  • the present invention is directed to compounds of formula (Xlla), (Xllb), (Xllc), (Xllt), (Xlllb), (Xlllh), (Xlll
  • R 16 is Si(Ph) 3 ,
  • R 1 , R 2 , R 3 and R 6 are a group of formula -(A ) 0 -(A 2 )p-(A 3 ) q -(A 4 )rR 16 , wherein 40
  • the present invention is directed to compounds of formula (la'), (lb'), (Ic'), or (Id'), wherein R 1 , R 2 , R 3 and R 6 are a group of formula -(Ai)o-(A2)p-(A3) q -(A4) r Ri6 , wherein -(Ai) 0 -(A 2 ) P -(A 3 ) q -(A4) r is a single bond, or a group of
  • R 3 and R 6 may be the same or different.
  • the present invention is directed to compounds of formula (le'), wherein R 3 and R 6 are the same, or different from each other and are a group of formula -(Ai) 0 -(A2) -(A 3 ) -(A4) r Ri 6 , wherein -(Ai) 0 -(A2) -(A 3 ) -(A4) r is a sin-
  • Halogen is fluorine, chlorine, bromine and iodine.
  • Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1 ,1 ,3,3,5,5- hexa methyl hexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-non
  • d-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2- ethylhexyl.
  • Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl.
  • Ci-C25alkoxy groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un- decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.
  • Examples of d-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2- dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1 ,1 ,3,3-tetramethylbutoxy and 2- ethylhexyloxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy.
  • cycloalkyl group is typically C5-Ci2cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
  • C6-C2 4 aryl which optionally can be substituted, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted.
  • Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-Cioaryl group.
  • C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ⁇ , ⁇ -dimethyl- o-phenyl-butyl, ⁇ -phenyl-dodecyl, ⁇ -phenyl-octadecyl, co-phenyl-eicosyl or ⁇ -phenyl-docosyl, preferably Cz-Cisaralkyl such as benzyl, 2-benzyl-2- propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ⁇ , ⁇ -dimethyl-co-phenyl-butyl, co-phenyl-dodecyl or ⁇ -phenyl-octadecyl, and particularly preferred C7-Ci2aral
  • C2-C3oheteroaryl represents a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated ⁇ -electrons such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzo- furanyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl,
  • Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2- a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Ci 4 heteroaryl group.
  • C6-C2 4 arylen groups which optionally can be substituted by G, are typically phenylene, 4- methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene, or 2- naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenan- thrylene, or anthrylene, which may be unsubstituted or substituted.
  • Preferred C6-C2 4 arylen groups are 1 ,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted.
  • C2-C3oheteroarylen groups which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated -electrons such as thienylene, benzothiophenylene, dibenzothio- phenylene, thianthrenylene, furylene, furfurylene, 2H-pyranylene, benzofuranylene, isoben- zofuranylene, dibenzofuranylene, phenoxythienylene, pyrrolylene, imidazolylene, pyrazol- ylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indoly
  • C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolylene, dibenzofuranylene and benzimidazo[1 ,2-a]benzimidazo-2,5-ylene
  • Ci-C4alkyl which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl.
  • Possible substituents of the above-mentioned groups are d-dalkyl, a hydroxyl group, a mercapto group, d-dalkoxy, d-dalkylthio, halogen, halo-d-dalkyl, or a cyano group.
  • the C6-C24aryl (d-dsaryl) and d-doheteroaryl groups are preferably substituted by one, or more d-dalkyl groups.
  • a substituent occurs more than one time in a group, it can be different in each occurrence.
  • Halo-d-dalkyl is an alkyl group where at least one of the hydrogen atoms is replaced by a halogen atom. Examples are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -(CF 2 ) 3 CF 3 , and -C(CF 3 ) 3 .
  • substituted by G means that one, or more, especially one to three substituents G might be present.
  • the aforementioned groups may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of groups containing at least 2 carbon atoms connected to one another by single bonds; d-dsaryl is not interrupted; interrupted arylalkyl contains the unit D in the alkyl moiety, d-dsalkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (Ch Ch O i-g- R x , where R* is H or d-doalkyl or d-doalkanoyl (e.g.
  • R y is d-dsalkyl, d-Ci2cycloalkyl, phenyl, C 7 -d 5 phenylalkyl, and R y ' embraces the same definitions as R y or is H ;
  • d-dalkylene-COO-R z e.g. CH 2 COOR z , CH(CH 3 )COOR z , C(CH 3 ) 2 COOR z , where R z is H , d-dsalkyl, (CH2CH20)i-9-R x , and R x embraces the definitions indicated above;
  • alkyl group substituted by E is, for example, an alkyl group where at least one of the hydrogen atoms is replaced by F. Examples are -CF3, -CF2CF3,
  • the halogenation can be performed by methods known to those skilled in the art. Preference is given to brominating or iodinating in the 3 and 6 positions (dibromination) or in the 3 or 6 positions (monobromination) of the base skeleton of the formula 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole).
  • Optionally substituted dibenzofurans, dibenzothiophenes and carbazoles can be dibromin- ated in the 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) with bromine or NBS in glacial acetic acid or in chloroform.
  • the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0°C.
  • Dibenzofuran (diben- zothiophene) can be monobrominated in the 3 position by a sequence known to those skilled in the art, comprising a nitration, reduction and subsequent Sandmeyer reaction.
  • Suitable bases are known to those skilled in the art and are preferably selected from the group consisting of alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2, alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH2, alkali metal or alkaline earth metal carbonates such as K2CO3 or CS2CO3, and alkali metal alkox- ides such as NaOMe, NaOEt.
  • alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2
  • alkali metal hydrides such as NaH, KH
  • alkali metal amides such as NaNH2
  • alkali metal or alkaline earth metal carbonates such as K2CO3 or CS2CO3
  • alkali metal alkox- ides such as NaOMe, NaOEt.
  • mixtures of the aforementioned bases are suitable. Particular preference is given to NaOH, KOH, NaH
  • Heteroarylation can be affected, for example, by copper-catalyzed coupling of
  • the N-arylation is, for example, disclosed in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001 ) 181 - 186 and Eur. J. Org. Chem. (2007) 2147-2151.
  • the reaction can be performed in solvent or in a melt.
  • Suitable solvents are, for example, (polar) aprotic solvents such as dimethyl sulfoxide, dimethylfor- mamide, N-methyl-2-pyrrolidone (NMP), tridecane or alcohols.
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and car- apeloles can be readily prepared by an increasing number of routes.
  • An overview of the synthetic routes is, for example, given in Angew. Chem. Int. Ed. 48 (2009) 9240 - 9261.
  • diboronic acid or diboronate group containing dibenzofurans, diben- zothiophenes, and carbazoles can be obtained by reactin
  • a catalyst such as, for example, [1 ,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), complex (Pd(CI)2(dppf)
  • a base such as, for example, potassium acetate
  • a solvent such as, for example, dimethyl formamide, dimethyl sulfoxide, diox
  • Y 1 is independently in each occurrence a Ci-Ci8alkylgroup and Y 2 is independently in each occurrence a C2-Cioalkylene group, such as -CY 3 Y 4 -CY 5 Y 6 -, or -CY7Y8-CY9Y10- CY Y 12 -, wherein Y 3 , Y 4 , Ys, ⁇ ⁇ , ⁇ ?, ⁇ ⁇ _ ⁇ ⁇ .
  • ⁇ and ⁇ 12 are independently of each other hydrogen, or a Ci-Ci8alkylgroup, especially -C(CH3)2C(CH3)2-, - C(CH3)2CH 2 C(CH 3 )2-, or -CH 2 C(CH 3 )2CH 2 -, and Y 13 and Y 14 are independently of each other hydrogen, or a Ci-Ci8alkylgroup.
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with alkyl lithium reagents, such as, for example, n-butyl lithium, or t-buthyl lithium, followed nic esters, such as, for example, B(isopropoxy)3,
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting dibenzofurans, dibenzothiophenes and carbazoles with lithium amides, such as, for example, lithium diisopropylamide (LDA) followed by esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • lithium amides such as, for example, lithium diisopropylamide (LDA) followed by esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • imidazo[1 ,2-a]imidazoles such as, for example and
  • the catalyst may be one of the ⁇ -halo(triisopropylphosphine)( ⁇ 3 -allyl)palladium(ll) type (see for example W099/47474).
  • the Suzuki reaction is carried out in the presence of an organic solvent, such as an aromatic hydrocarbon or a usual polar organic solvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixtures thereof, most preferred toluene.
  • an organic solvent such as an aromatic hydrocarbon or a usual polar organic solvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixtures thereof, most preferred toluene.
  • the amount of the solvent is chosen in the range of from 1 to 10 I per mol of boronic acid derivative.
  • the reaction is carried out under an inert atmosphere such as nitrogen, or argon.
  • an aqueous base such as an alkali metal hydroxide or carbonate such as NaOH, KOH, Na2C03, K2CO3, Cs2C03 and the like, preferably an aqueous K2CO3 solution is chosen.
  • the molar ratio of the base to boronic acid or boronic ester derivative is chosen in the range of from 0.5:1 to 50:1 , very especially 1 :1.
  • the reaction temperature is chosen in the range of from 40 to 180°C, preferably under reflux conditions.
  • the reaction time is chosen in the range of from 1 to 80 hours, more preferably from 20 to 72 hours.
  • a usual catalyst for coupling reactions or for polycondensation reactions is used, preferably Pd-based, which is described in WO2007/101820.
  • the palladium compound is added in a ratio of from 1 :10000 to 1 :50, preferably from 1 :5000 to 1 :200, based on the number of bonds to be closed. Preference is given, for example, to the use of palla- dium(ll) salts such as PdAc2 or Pd2dba3 d from the
  • the ligand is added in a ratio of from 1 : 1 to 1 :10, based on Pd.
  • the catalyst is added as in solution or suspension.
  • an appropriate organic solvent such as the ones described above, preferably benzene, toluene, xylene, THF, dioxane, more preferably toluene, or mixtures thereof, is used.
  • the amount of solvent usually is chosen in the range of from 1 to 10 I per mol of boronic acid derivative.
  • Organic bases such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Lead- beater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).
  • phase transfer catalysts such as, for example TBAB
  • Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, G. Wegner in Macromol. Rap- id Commun. 17 (1996) 239-252 and G. A. Molander und B. Canturk, Angew. Chem. , 121 (2009) 9404 - 9425.
  • JP2011084531 describes, for example, the synthesis of benzofuro[3,2-b]pyridine in two steps starting from 2-bromopyridin-3-ol using a base catalyzed cyclisation. The brominated ation with bromine in the presence of silver sulfate.
  • US2010/0187984 describes, for example, the synthesis of 3,6-dichloro-benzofuro[2,3- b]pyridine in three steps starting from 2-amino-5-chloropyridine using a cyclisation of a dia- zoniumion salt.
  • JP2002284862 describes the syntheses of 2,7-dibromo-furo[3,2-b:4,5-b]dipyridine starting from 2-(3-amino-5-bromo-2-pyridyl)-5-bromo-pyridin-3-amine using an acid catalyzed cy- clisation of a diazoniumion salt.
  • the synthesis of the starting material is described by Y. F
  • halogenation can be performed by methods known to those skilled in the art.
  • 4-lodobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting enzimidazo- lo[2,1-b][1 ,3]benzothiazole with butyl lithium and I2 in tetra arylation can
  • 4-iodobenzimidazolo[2,1-b][1 ,3]benzothiazole Ullmann reaction.
  • 4-Chlorobenzimidazolo[2,1-b][1 ,3]benzothiazole can be prepared as described in Organic &
  • 2-lodobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting benzimidazo- lo[2,1-b][1 ,3]benzothiazole in CH 3 COOH and CF3COOH in the presence of N- iodosuccinimide (NIS).
  • NIS N- iodosuccinimide
  • 2-Bromobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting 2- mercaptobenzimidazole and 1 ,4-dibromo-2-nitro-benzene in the presence of caesiu bonate in DMSO (dimethyl sulfoxide).
  • 2-Bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting 2- bromobenzimidazolo[2,1-b][1 ,3]benzothiazole with N-iodosuccinimide (NIS) in acetic acid in the presence of trifluoroacetic acid,
  • NIS N-iodosuccinimide
  • the above compound can also be prepared by Suzuki coupling of 9- iodobenzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[8-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole (WO2012130709).
  • compounds of formula I can be obtained by reacting a compound of formula X with 1 ,3-dihydrobenzimidazole-2-thione in the presence of a base, such as, for example, CS2CO3, in a solvent, such as, for example, dimethylsulfoxide, at elevated temperatures, especially 130 to 170 °C.
  • a base such as, for example, CS2CO3
  • a solvent such as, for example, dimethylsulfoxide
  • Examples 1 to 3 It has been found that the compounds of the formula I are particularly suitable for use in applications in which charge carrier conductivity is required, especially for use in organic electronics applications, for example selected from switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs), the compounds of the formula I being particularly suitable in OLEDs for use as matrix material in a light-emitting layer and/or as electron and/or exciton blocker material and/or as hole and/or exciton blocker material, especially in combination with a phosphorescence emitter.
  • switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs)
  • OLEDs organic light- emitting diodes
  • inventive compounds of the formula I are suitable especially for use as matrix and/or charge/exciton blocker materials for blue and green emitters, for example light blue or deep blue emitters, these being especially phosphorescence emitters.
  • the compounds of the formula I can be used as conductor/complementary materials in organic electronics applications selected from switching elements and organic solar cells.
  • the compounds of the formula I can be used as matrix material and/or charge/exciton blocker material and/or charge transport material (charge conductor material).
  • inventive compounds of the formula I are preferably used as matrix materials in organic electronics applications, especially in OLEDs.
  • an emitter material In the emission layer or one of the emission layers of an OLED, it is also possible to combine an emitter material with a matrix material of the compound of the formula I and a further matrix material which has, for example, a good hole transport property. This achieves a high quantum efficiency of this emission layer.
  • a compound of the formula I is used as matrix (host) material in an emission layer and additionally as charge/exciton blocker material, owing to the chemical identity or similarity of the materials, an improved interface between the emission layer and the adjacent charge/exciton blocker material, which can lead to a decrease in the voltage with equal luminance and to an extension of the lifetime of the OLED.
  • the use of the same material for charge/exciton blocker material and for the matrix of an emission layer allows the production process of an OLED to be simplified, since the same source can be used for the vapor deposition process of the material of one of the compounds of the formula I.
  • Suitable structures of organic electronic devices are known to those skilled in the art and are specified below.
  • the organic transistor generally includes a semiconductor layer formed from an organic layer with charge transport capacity; a gate electrode formed from a conductive layer; and an insulat- ing layer introduced between the semiconductor layer and the conductive layer. A source electrode and a drain electrode are mounted on this arrangement in order thus to produce the transistor element. In addition, further layers known to those skilled in the art may be present in the organic transistor.
  • the organic solar cell photoelectric conversion element
  • the organic layer generally comprises an organic layer present between two plate-type electrodes arranged in parallel.
  • the organic layer may be configured on a comb-type electrode. There is no particular restriction regarding the site of the organic layer and there is no particular restriction regarding the material of the electrodes.
  • At least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode.
  • the organic layer is formed from two sublayers, i.e. a layer with p-type semiconductor properties or hole transport capacity, and a layer formed with n-type semiconductor properties or charge transport capacity.
  • the layers with charge transport capacity may com- prise the compounds of formula I.
  • the present invention further provides an organic light-emitting diode comprising an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i), and if appropriate at least one further layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for elec- trons/excitons, at least one hole injection layer, at least one hole transport layer, at least one electron injection layer and at least one electron transport layer, wherein the at least one compound of the formula I is present in the light-emitting layer (e) and/or in at least one of the further layers.
  • the at least one compound of the formula I is preferably present in the light-emitting layer and/or the charge/exciton blocking layers
  • At least one compound of the formula I is used as charge transport material.
  • a compound of the formula la, lb, Ic, Id, or le is used as charge transport material.
  • Examples of preferred compounds of formula I are compounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G-1 to E-20 shown above.
  • At least one compound of the formula I is used as charge/exciton blocker material.
  • a compound of the formula la, lb, Ic, Id, or le is used as charge/exciton blocker material.
  • preferred compounds of formula I are compounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G-1 to E-20 shown above.
  • the present application further relates to a light-emitting layer comprising at least one compound of the formula I.
  • the inventive organic light-emitting diode thus generally has the following structure:
  • the inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:
  • Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art.
  • the OLED does not have all of the layers mentioned; for example, an OLED with layers (a) (anode), (e) (light-emitting layer) and (i) (cathode) is likewise suitable, in which case the functions of the layers (c) (hole transport layer) and (f) (blocking layer for holes/excitons) and (g) (electron transport layer) are assumed by the adjacent layers.
  • OLEDs which have layers (a), (c), (e) and (i), or layers (a), (e), (f), (g) and (i), are likewise suitable.
  • the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light- emitting layer (e).
  • a plurality of the aforementioned functions are combined in one layer and are assumed, for example, by a single material present in this layer.
  • a material used in the hole transport layer in one embodiment, may simultaneously block excitons and/or electrons.
  • the individual layers of the OLED among those specified above may in turn be formed from two or more layers.
  • the hole transport layer may be formed from a layer into which holes are injected from the electrode, and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer.
  • the electron conduction layer may likewise consist of a plurality of layers, for example a layer in which electrons are injected by the electrode, and a layer which receives electrons from the electron injection layer and transports them into the light-emitting layer.
  • These layers mentioned are each selected according to factors such as energy level, thermal resistance and charge carrier mobility, and also energy difference of the layers specified with the organic layers or the metal electrodes.
  • the person skilled in the art is capable of selecting the structure of the OLEDs such that it is matched optimally to the organic compounds used in accordance with the invention.
  • the anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 11 , 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (a) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol.
  • Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals.
  • Anode (and substrate) may be sufficiently transparent to create a bottom-emitting device.
  • a preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate).
  • a reflective anode may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed. Other anode materials and structures may be used.
  • injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or a charge generating layer, into an adjacent organic layer. Injection layers may also perform a charge transport function.
  • the hole injection layer may be any layer that improves the injection of holes from anode into an adjacent organic layer.
  • a hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, or it may be a vapor deposited small molecule material, such as, for example, CuPc or MTDATA.
  • Polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-diyl) (Plexcore ® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS.
  • PVK poly(N-vinylcarbazole)
  • polythiophenes polypyrrole
  • polyaniline polyaniline
  • self-doping polymers such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-di
  • hole transport material Either hole-transporting molecules or polymers may be used as the hole transport material.
  • Suitable hole transport materials for layer (c) of the inventive OLED are disclosed, for ex- ample, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996, US20070278938, US2008/0106190, US201 1/0163302 (triarylamines with (di)benzothiophen/(di)benzofuran; Nan-Xing Hu et al. Synth. Met. 1 11 (2000) 421 (in- dolocarbazoles), WO2010002850 (substituted phenylamine compounds) and
  • WO2012/16601 in particular the hole transport materials mentioned on pages 16 and 17 of WO2012/16601. Combination of different hole transport material may be used.
  • polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PE- DOT/PSS.
  • PVK poly(N-vinylcarbazole)
  • polythiophenes polypyrrole
  • polyaniline polyaniline
  • self-doping polymers such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl)
  • metal carbene complexes as hole transport materials.
  • Suitable carbene complexes are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418 A2, WO2005/1 13704, WO2007/115970,
  • the hole-transporting layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No.
  • mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example M0O2, M0O3, WO x , ReCb and/or V2O5, preferably M0O3 and/or ReCb, more pref- erably M0O3, or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6- tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8- tetracyanoquinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 1 1 ,
  • the hole transport layer comprises from 0.1 to 10 wt % of M0O3 and 90 to 99.9 wt % carbene complex, especially of the carbene complex HTM-1 , wherein the total amount of the M0O3 and the carbene com- plex is 100 wt %.
  • Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer.
  • An electron/exciton blocking layer (d) may be disposed between the first emitting layer (e) and the hole transport layer (c), to block electrons from emitting layer (e) in the direction of hole transport layer (c).
  • Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
  • Suitable metal complexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, W02006/056418 A2, WO2005/113704, WO2007/115970, WO2007/115981 and WO2008/000727.
  • the light-emitting layer (e) comprises at least one emitter material. In principle, it may be a fluorescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art.
  • the at least one emitter material is preferably a phosphorescence emitter.
  • the phosphorescence emitter compounds used with preference are based on metal com- plexes, and especially the complexes of the metals Ru, Rh, Ir, Pd and Pt, in particular the complexes of Ir, have gained significance.
  • the compounds of the formula I can be used as the matrix in the light-emitting layer.
  • Suitable metal complexes for use in the inventive OLEDs are described, for example, in documents WO 02/60910 A1 , US 2001/0015432 A1 , US 2001/0019782 A1 ,
  • WO 2005/113704 A2 WO 2006/1 15301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 2006121811 A1 , WO 2007095118 A2, WO 2007/115970, WO 2007/115981 ,
  • metal complexes are the commercially available metal complexes tris(2- phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C 2 '), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l-phenylisoquinoline), iridium(lll) bis(2,2'-benzothienyl)pyridinato-N,C 3 ')(acetylacetonate), tris(2-phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-N,C 2 )picolinate, iridium(lll) bis(1- phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acett
  • Preferred phosphorescence emitters are carbine complexes. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727, WO2009050281 , WO2009050290, WO2011051404, US2011/057559 WO2011/073149, WO2012/121936A2,
  • the light emitting layer (e) comprises at least one carbine complex as phosphorescence emitter.
  • Suitable carbine complexes are, for example, compounds of the
  • M is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the respective metal atom;
  • Carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;
  • L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
  • K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a ⁇ complex with M 1 ; n1 is the number of carbene ligands, where n1 is at least 1 and when n1 > 1 the carbene ligands in the complex of the formula I can be identical or different;
  • nl is the number of ligands L, where ml can be 0 or ⁇ 1 and when ml > 1 the ligands L can be identical or different;
  • o is the number of ligands K, where o can be 0 or ⁇ 1 and when o > 1 the ligands K can be identical or different;
  • n1 + ml + o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n1 is at least 1.
  • M is Ir, or Pt
  • n1 is an integer selected from 1 , 2 and 3,
  • Y is N R 51 , O, S or C(R25) 2 ,
  • R 51 is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical op- tionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
  • R5s are eac h, jf A 2 ', A 3 ', A 4 ' and/or A 5 ' is N, a free electron pair, or, if A 2 ', A 3' , A 4' and/or A 5' is C, each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one het- eroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms
  • R 53 and R 54 together with A 3' and A 4' form an optionally substituted, unsaturated ring optionally interrupted by at least one further heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms,
  • R 56 , R 57 , R 58 and R 59 are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, cycloheteroalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
  • R 56 and R 57 , R 57 and R 58 or R 58 and R 59 together with the carbon atoms to which they are bonded, form a saturated, unsaturated or aromatic, optionally substituted ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms, and/or
  • R 55 and R 56 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, an aromatic unit, heteroaromatic unit and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which is optionally fused a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms,
  • R 25 is independently a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon at- oms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
  • K is an uncharged mono- or bidentate ligand
  • L is a mono- or dianionic ligand, preferably monoanionic ligand, which may be mono- or bidentate,
  • ml is 0, 1 or 2, where, when ml is 2, the K ligands may be the same or different, o1 is 0, 1 or 2, where, when o1 is 2, the L ligands may be the same or different.
  • the compound of formula IX is more preferably a compound (BE-1 ), (BE-2), (BE-7), (BE- 12), (BE-16), (BE-64), or (BE-70).
  • the most preferred phosphorescent blue emitters are compounds (BE-1 ) and (BE-12).
  • the homoleptic metal-carbene complexes may be present in the form of facial or meridional isomers, preference being given to the facial isomers.
  • Suitable carbene complexes of formula (IX) and their preparation process are, for example, described in WO201 1/073149.
  • the compounds of the present invention can also be used as host for phosphorescent green emitters.
  • Suitable phosphorescent green emitters are, for example, specified in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151 , US20110227049, WO201 1090535, WO2012/08881 , WO20100056669, WO20100118029, WO20100244004, WO201 1109042, WO2012166608, US20120292600, EP2551933A1 ; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO 2012053627; US6921915, US20090039776; and JP2007123392.
  • the light-emitting layer may comprise further components in addition to the emitter materi- al.
  • a fluroescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material.
  • a matrix material can be used. This matrix material may be a polymer, for example poly(N- vinylcarbazole) or polysilane.
  • At least one compound of the formula I is used as matrix material.
  • a compound of the formula la, lb, lc, Id, or le is used as matrix material.
  • preferred compounds of formula I are com- pounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G- 1 to E-20 shown above.
  • the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of at least one of the aforementioned emitter materials and 60 to 98% by weight, preferably 75 to 95% by weight, of at least one of the aforementioned ma- trix materials - in one embodiment at least one compound of the formula I - where the sum total of the emitter material and of the matrix material adds up to 100% by weight.
  • Suitable metal complexes for use together with the compounds of the formula I as matrix material in OLEDs are, for example, also carbene complexes as described in
  • WO2007108459 H-1 to H-37
  • H-20 to H-22 and H-32 to H-37 most preferably H-20, H-32, H-36, H-37
  • WO2008035571 A1 Host 1 to Host 6
  • JP2010135467 compounds 1 to 46 and Host-1 to Host-39 and Host-43
  • WO2009008100 compounds No.1 to No.67 preferably No.3, No.4, No.7 to No. 12, No.55, No.59, No. 63 to No.67, more preferably No. 4, No. 8 to No. 12, No.
  • WO2007119816 the compounds 1 to 37, WO2010087222 the compounds H-1 to H-31 , WO2010095564 the compounds HOST-1 to HOST-61 , WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446, WO06128800, WO2012014621 ,
  • the above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules. 72 (for example,
  • X is NR, S, O or PR
  • R is aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi;
  • R221 R222 anc are independently of each other aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi, wherein at least on of the groups R 221 , R 222 , or R 223 is aryl, or heteroaryl;
  • R 224 and R 225 are independently of each other alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl, a group A 200 , or a group having donor, or acceptor characteristics;
  • n2 and m2 are independently of each other 0, 1 , 2, or 3;
  • R 206 and R 207 form together with the nitrogen atom a cyclic residue having 3 to 10 ring atoms, which can be unsubstituted, or which can be substituted with one, or more substitu- ents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and/or which can be annulated with one, or more further cyclic residues having 3 to 10 ring atoms, wherein the annulated residues can be unsubstituted, or can be substituted with one, or more substituents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and R208 i R209 i R2io_ 2i i _ 212_ 213_ R214 u nc
  • R215 are independently of each other aryl, het
  • T is O, or S, preferably O. If T occurs more than one time in a molecule, all groups T have the same meaning.
  • Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer.
  • the hole blocking layer may be disposed between the emitting layer (e) and electron transport layer (g), to block holes from leaving layer (e) in the direction of electron transport layer (g).
  • Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
  • Additional hole blocker materials typically used in OLEDs are 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline (bathocuproin, (BCP)), bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll) (BAIq), phenothiazine S,S-dioxide derivates and 1 ,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-transport material.
  • mCPy 2,6-bis(N-carbazolyl)pyridine
  • BCP 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline
  • BAIq bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll)
  • BAIq bis(
  • hole blockers and/or electron conductor materials are 2,2',2"-(1 ,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4- biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole, 8-hydroxyquinolinolatolithium, 4- (naphthalen-1-yl)-3,5-diphenyl-4H-1 ,2,4-triazole, 1 ,3-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4- oxadiazo-5-yl] benzene, 4,7-diphenyl-1 ,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-1 ,2,4-triazole, 6,6'-bis[5-(biphenyl-4-yl)-1 ,3,4
  • disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, dis- ilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and dis- ilylbenzothiophene S,S-dioxides, as specified, for example, in PCT applications
  • compounds (SH-1 ), (SH-2), (SH-3), SH-4, SH-5, SH-6, (SH-7), (SH-8), (SH-9) and (SH-10) may be used as hole/exciton blocking materials.
  • Electron transport layer may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity.
  • EP1970371 or in EP1097981 , and azole compounds such as 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole (TAZ).
  • PBD 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole
  • TEZ 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole
  • At least one phenanthroline compound is used, preferably BCP, or at least one pyridine compound according to the formula (VIII) below, preferably a compound of the formula (Vlllaa) below.
  • alkaline earth metal or alkali metal hy- droxyquinolate complexes for example Liq
  • Suitable alkaline earth metal or alkali metal hydroxyquinolate complexes are specified below (formula VII). Reference is made to WO2011/157779.
  • the electron-transport layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1 , 1 July 2003 (p- doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No.
  • n-Doping is achieved by the addition of reducing materials.
  • mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, CS2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li 3 N, Rb 2 C0 3 , dipotassium phthalate, W(hpp) 4 from EP1786050, or with compounds described in EP1837926B1 , EP1837927, EP2246862 and WO2010132236.
  • alkali/alkaline earth metals or alkali/alkaline earth metal salts for example Li, Cs, Ca, Sr, CS2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq)
  • the electron-transport layer comprises at least one compound of the general formula (VII)
  • R 32 and R 33 are each independently F, d-Cs-alkyl, or C6-Ci 4 -aryl, which is optionally substituted by one or more d-Cs-alkyl groups, or
  • R 32 and/or R 33 substituents together form a fused benzene ring which is optionally substituted by one or more d-Cs-alkyl groups;
  • a and b are each independently 0, or 1 , 2 or 3,
  • M 1 is an alkaline metal atom or alkaline earth metal atom
  • p is 1 when M 1 is an alkali metal atom, p is 2 when M 1 is an earth alkali metal atom.
  • a very particularly preferred compound of the formula (VII) is (Liq), which may be present as a single species, or in other forms such as Li g Q g in which g is an integer, for example LkQe- Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.
  • the electron-transport layer comprises at least one compound of the formul
  • R 34 , R 35 , R 36 , R 37 , R 34' , R 3 5', R36' and R 37' are each independently H , Ci-Cis-alkyl, C1-C18- alkyl which is substituted by E and/or interrupted by D, C6-C2 4 -aryl, C6-C2 4 -aryl which is substituted by G, C2-C2o-heteroaryl or C2-C2o-heteroaryl which is substituted by G, Q is an arylene or heteroarylene group, each of which is optionally substituted by G;
  • E is -OR 44 ; -SR 44 ; -NR 4 0R 4 i ; -COR 43 ; -COOR 42 ; -CONR 4 0R 4 i ; -CN; or F;
  • G is E, Ci-Ci8-alkyl, Ci-Cis-alkyl which is interrupted by D , Ci-Ci8-perfluoroalkyl, C1-C18- alkoxy, or Ci-Cis-alkoxy which is substituted by E and/or interrupted by D,
  • R 38 and R 39 are each independently H , C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-;
  • R 40 and R 41 are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; or
  • R 40 and R 41 together form a 6-membered ring
  • R 42 and R 43 are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
  • R 44 is C6-Ci8-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; C1-C18- alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
  • R 45 and R 46 are each independently Ci-Cie-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl,
  • R 47 is Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl.
  • Preferred compounds of the formula (VIII) are compounds of the formula (Villa)
  • R 48 is H or Ci-Cis-alkyl
  • R 48 ' is H , Ci-Cis-alkyl or or
  • the electron-transport layer comprises a compound Liq and a compound ETM-2.
  • the electron-transport layer comprises the compound of the formula (VII) in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of the compounds of the formulae (VII) and the amount of the compounds of the formulae (VIII) adds up to a total of 100% by weight.
  • the electron-transport layer comprises Liq in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of Liq and the amount of the dibenzofuran compound(s), especially ETM-1 , adds up to a total of 100% by weight.
  • the electron-transport layer comprises at least one phenanthro- line derivative and/or pyridine derivative.
  • the electron-transport layer comprises at least one phe- nanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex.
  • the electron-transport layer comprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790, especially ETM-1.
  • the electron-transport layer comprises a compound described in WO2012/11 1462, WO2012/147397, WO2012014621 , such as, for example, a
  • the electron injection layer may be any layer that improves the injection of electrons into an adjacent organic layer.
  • Lithium-comprising organometallic compounds such as 8- hydroxyquinolatolithium (Liq), CsF, NaF, KF, CS2CO3 or LiF may be applied between the electron transport layer (g) and the cathode (i) as an electron injection layer (h) in order to reduce the operating voltage.
  • the cathode (i) is an electrode which serves to introduce electrons or negative charge carriers.
  • the cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1 , for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
  • the different layers if present, have the following thicknesses:
  • anode 500 to 5000 A (angstrom), preferably 1000 to 2000 A;
  • Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
  • the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport.
  • the selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.
  • the inventive OLED can be produced by methods known to those skilled in the art.
  • the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate.
  • Suitable substrates are, for example, glass, inorganic semi- conductors or polymer films.
  • vapor deposition it is possible to use customary techniques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
  • the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art.
  • the compounds of the formula I in at least one layer of the OLED preferably in the light-emitting layer (preferably as a matrix material), charge transport layer and/or in the charge/exciton blocking layer makes it possible to obtain OLEDs with high efficiency and with low use and operating voltage.
  • the OLEDs obtained by the use of the compounds of the formula I additionally have high lifetimes.
  • the efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs. For example, high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermediate layer of LiF, can be used.
  • additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence.
  • the OLEDs may further comprise at least one second light-emitting layer.
  • the overall emission of the OLEDs may be composed of the emission of the at least two light-emitting layers and may also comprise white light.
  • the OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels.
  • Mobile visual display units are, for example, visual dis- play units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains.
  • inventive OLEDs are, for example, keyboards; items of clothing; furniture; wallpaper.
  • the present invention relates to a device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
  • Example 1a) is repeated, except that instead of 6H-benzimidazolo[1 ,2-a]benzimidazole 9H-carabazole is used.
  • Example 1a) is repeated, except that instead of the product of Example 1 a) the product of Example 2a) is used.
  • N-iodosuccinimide N-iodosuccinimide
  • 2- bromobenzimidazolo[2,1-b][1 ,3]benzothiazole 175 ml acetic acid and 9 ml trifluoroacetic acid at 100 °C under nitrogen.
  • the product is stirred for 2.5 g at 100 °C and the precipitated product is filtered off.
  • the product is washed with a 10 % sodium dithionite solution, water and methanol.
  • the product is soxhlet extracted with 300 ml methyl ethyl ketone and the product is filtered off (yield: 15.1 g (82 %)).
  • the reaction mixture is stirred at 100 °C under nitrogen for 75 h and then filtered on Hyflo Super Cel (CAS number 91053-39-3) with dichloromethane.
  • the di- chloromethane is distilled off and the solution is poured into methanol.
  • the product is filtered off, filtered on silica gel with dichloromethane and then dichloromethane/ethanol 95/5.
  • the solvent is concentrated to a volume of 10 ml ethanol. 100 ml methanol are added and the product is filtered off (yield: 6.38 g (49 %)).
  • 2,9-di(dibenzofuran-4-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 2-bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole and dibenzofuran-4-ylboronic acid.
  • 2,9-di(dibenzofuran-4-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[8-(4,4,5,5- tetramethyl-1 ,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole.
  • 9-[8-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole is prepared as described in
  • the triplet energies of the materials are directly determined from the onsets of the ured phosphorescence spectra of the thin films of neat materials.
  • the 2% in PMMA films are prepared by dissolving 1 mg of the respective material in 370 ⁇ of a dichloromethane solution containing 10 wt% PMMA.
  • Compound (B-1 ) is deposited by vapor deposition to the quartz substrates at a rate of approx. 0.5-5 nm/min at about 10- 6 mbar until approx. 60 nm thick film is formed.
  • the resulting thin film samples are inserted into a liquid-helium cryostat Optistat CF (Oxford Instruments) and cooled to a temperature of 4-5K.
  • the phosphorescence spectra are measured with a fluorescence/phosphorescence spectrometer FLS- 920P (Edinburgh Instruments).
  • the samples are excited with an electrically pulsed LED model UVTOP 315-HL-T039 (Fa. Roithner, Vienna) with a center wavelength of 320 nm and a pulse width of 5 ⁇ .
  • the emission spectra are detected via time-gated spectroscopy with a delay-time of 260 ⁇ is.
  • the triplet energies (Ti) are determined from the onset of the phosphorescence spectra, the results are shown in the table below.
  • Compound F-12 has a higher triplet energy than comparative compound CC-1 . That is, compound F-12 is, in principal, a better host for deep blue phosphorescent emitters.
  • Cyclic voltammetry and differential pulsed voltammetry are performed using a computer- controlled Metrohm Autolab PGSTAT12 potentiostat in a three-electrode single- compartment cell with a platinum or glassy carbon working electrode, a platinum wire counter electrode and an Ag/AgCI or Ag/Ag + reference electrode.
  • Anhydrous DMF (distilled over P2O5) is used as the solvent under an inert atmosphere, and 0.1 M tetra-n-butylammonium hexafluorophosphate (TBAPF6) is used as the supporting electrolyte.
  • TAPF6 tetra-n-butylammonium hexafluorophosphate
  • the samples are measured at a concentration of 1 mM. All potentials are internally referenced to the ferro- cene/ferrocenium (Fc/Fc + ) couple.
  • IP ionization potential
  • EA electron affinity
  • IP [eV] 1.4x(1.0xE 0 nset - Fc/Fc + E 0 nset) + 4.6 ⁇ Org. El. 2005, 6, 1 1-20) and
  • the electron affinity of the benzimidazolo[2,1-b][1 ,3]benzothiazole derivatives, such as, for example, compound B-2, of the present invention is higher than the electron affinity of corresponding 6H-benzimidazolo[1 ,2-a]benzimidazole derivatives, such as, for example, comparative compound CC-2.
  • the ionization potential of the benzimidazolo[2,1- b][1 ,3]benzothiazole derivatives of the present invention is also lower (higher absolute value) than the ionization potential of corresponding 6H-benzimidazolo[1 ,2-a]benzimidazole derivatives.
  • the benzimidazolo[2,1-b][1 ,3]benzothiazoles of the present application are in general superior electron injection, hole blocking and electron transporting units in comparison with benzimidazolo[1 ,2-a]benzimidazoles of the prior art.
  • the ITO substrate used as the anode is first cleaned with an isopropanol in an ultrasonic bath. To eliminate any possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for further 30 minutes. This treatment also improves the hole injection properties of the ITO. Then Plexcore® OC AJ20-1000 (commercially available from Plextronics Inc.) is spin-coated and dried to form a hole injection layer (-40 nm). Thereafter, the organic materials specified below are applied by vapor deposition to the Plexcore® coated substrate at a rate of approx. 0.5-5 nm/min at about 10- 7 -10- 9 mbar. As a
  • hole transport material compound (HTM-1 ; for preparation, see Ir com- plex (7) in the application WO2005/019373) is applied by vapor deposition in a thickness of 10 nm doped with MoOx (-10%) to improve the conductivity.
  • EQE External quantum efficiency

Abstract

The present invention relates to compounds of formula (I), a process for their production and their use in electronic devices, especially electroluminescent devices. When used as charge transport material and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula (I) may provide improved efficiency, stability, manufacturability and/or spectral characteristics of electroluminescent devices.

Description

Benzimidazolo[2,1-b][1 ,3]benzothiazoles for electronic applications
Description
The present invention relates to compounds of formula I, a process for their production and their use in electronic devices, especially electroluminescent devices. When used as charge transport material and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency, stability, manufacturability and/or spectral characteristics of electroluminescent devices.
WO2012139692 relates to electronic devices which comprise an anode, a cathode and at least one organic layer, where the organic layer comprises one or more substituted ben
Figure imgf000002_0001
zene com ounds of formula (I), or
Figure imgf000002_0002
(II). Y can be S and n can be 0 or 1 , Z is
CR1 or N. R1 can be an aromatic or hetero aromatic ring system. DE102012000064 describes compounds of formula
Figure imgf000003_0001
(1 ) and their use in organic light emitting devices (OLEDs). Among others X can be C. If X is C, n is 1.
Figure imgf000003_0002
WO20121 10182 describes compounds of formula (I),
Figure imgf000003_0003
(II) and (III) and their use in electronic devices, especially OLEDs. X and Y can be S and Z is CR2, or N.
Figure imgf000003_0004
US20050074632 relates to compounds of formula (1 ), wherein
Figure imgf000003_0005
B is
Figure imgf000003_0006
and their use in OLEDs.
US20050079387 relates to compounds of formula Ai-A2-A3 (1 ), wherein
Figure imgf000004_0001
X and X' can be S, O, or Se. The compounds of formula A1-A2-A3 CI ) are used as blue luminescent material or as hosts for phosphorescent, or fluorecent dopants.
Figure imgf000004_0002
US2790172 relates to compounds of formula , wherein R and R1 are H, lower alkyl, lower alkoxy, or phenyl; or R1 and R can form a 6 membered carbocylcle; and a process for their production.
The synthesis of benzimidazolo[2,1-b][1 ,3]benzothiazole derivatives is described, for example, in the following documents:
- Zhang, Xinhai; Jia, Jiong; Ma, Chen; Organic + Biomolecular Chemistry 10 (2012) 7944- 79
Figure imgf000004_0003
X = F, CI
Y = F, N02
EWG is an elecron withdrawing group, like CN, NO2, CI, F, or CF3 and R is NO2, or OMe.
- Z. Wu et al., Eur. J. Org. Chem. (2011) 5242-5245:
Figure imgf000005_0001
I. G. Abramov et al., Chemistry of Heterocyclic Compounds 36 (2000) 1062:
Figure imgf000005_0002
Bulletin of the Chemical Society of Japan 55 (1982) 1681-1682:
Figure imgf000005_0003
J. J. D'Amico et al., J. Org. Chem. 42 (1977) 601 :
Figure imgf000005_0004
- J. Gao et al., Tetrahedron Letters 55 (2014) 3367-3373 relates to the synthesis of ben- zimidazo[2,1-£>]benzothiazole derivatives through sequential Cu-catalyzed domino coupling and Pd-catalyzed Suzuki reaction.
Figure imgf000005_0005
(Y = N, CH; Ri = H, CH3, i-Pr, F, CI, CN; R2 = H, CH3, OCH3, CI, N02)
For example, the synthesis of the following halo-containing benzimidazo[2,1- £>]benzothiazoles is described:
Figure imgf000005_0006
Figure imgf000006_0001
Figure imgf000006_0002
WO201 1160757 relates to an electronic device comprising an anode, cathode and at least
RYV R°
one organic layer which contains a compound of formulae (I),
Figure imgf000006_0003
(IV), wherein X may be a single bond and L may be a divalent group. The following 4H-lmidazo[1 ,2-a]imidazole compounds are explicitly disclosed:
Figure imgf000006_0004
such
Figure imgf000007_0001
as, for example, , a process for their production and their use in electronic devices, especially electroluminescent devices.
WO2013/050401 describes 4H-imidazo[1 ,2-a]imidazoles of formula
Figure imgf000007_0002
wherein X6 is -N= and X7 is -NR6-, or X7 is =N- and X6 is -NR6-, R6 is a group of formula
Figure imgf000007_0003
such as, for example,
Figure imgf000008_0001
; a process for their production and their use in electronic devices, especially electroluminescent devices.
WO2014/009317 relates to compounds of formula
Figure imgf000008_0002
(I), a process for their production and their use in electronic devices, especially electroluminescent devices. When used as host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency, stability, manufac- turability, or spectral characteristics of electrolumine
Figure imgf000008_0003
WO2014/044722 relates to compounds of formula (I), which are characterized in that they substituted by benzimidazo[1 ,2-a]benzimidazo-5-yl and/or benzimidazo[1 ,2-a]benzimidazo-2,5-ylene groups and in that at least one of the substitu- ents B1, B2, B3, B4, B5, B6, B7 and B8 represents N; a process for their production and their use in electronic devices, especially electroluminescent devices.
Notwithstanding these developments, there remains a need for organic light emitting devic- es comprising new charge transport materials to provide improved efficiency, stability, manufacturability, and/or spectral characteristics of electroluminescent devices.
Accordingly, it is an object of the present invention, with respect to the aforementioned prior art, to provide further materials suitable for use in OLEDs and further applications in organ- ic electronics. More particularly, it should be possible to provide charge transport materials, charge/exciton blocker materials and matrix materials for use in OLEDs. The materials should be suitable especially for OLEDs which comprise at least one phosphorescence emitter, especially at least one green emitter or at least one blue emitter. Furthermore, the materials should be suitable for providing OLEDs which ensure good efficiencies, good operative lifetimes and a high stability to thermal stress, and a low use and operating voltage of the OLEDs.
Certain benzimidazolo[2,1-b][1 ,3]benzothiazole derivatives are found to be suitable for use in organo-electroluminescent devices. In particular, said derivatives are suitable charge transport materials, or host materials for phosphorescent emitters with good efficiency and durability.
In OLEDs hole and electrons must be transported. To construct hole transporters and bipo- lar hosts, hole transporting units are required. For the preparation of electron transporters and bipolar hosts, electron transporting units are required. The benzimidazolo[1 ,2- ajbenzimidazole basic skeleton described in WO2011160757 represents a hole transporter unit, which is responsible for good hole transport and hole injection. It has surprisingly been found that the benzimidazolo[2,1-b][1 ,3]benzothiazole basic skeleton described in the pre- sent application represents an electron transporting unit, which is responsible for good electron transport and electron injection.
S nds of the formula
Figure imgf000009_0001
(I), wherein
Y1 and Y2 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally be substituted by G;
d is 0, or 1 ; c is 0, or 1 ;
R1 and R6 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a group of formula -(AV(A2)p-(A3)q-(A4)rR16,
a is 0, 1 , 2, or 3; b is 0, 1 , 2, or 3;
o is 0, or 1 , p is 0, or 1 , q is 0, or 1 , r is 0, or 1 ,
A1, A2, A3 and A4 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, or a C2-C3oheteroarylen group, which can optionally be substituted by G;
R16 is H, -NR10R11 , or -Si(R12)(R13)(R14), a C6-C24aryl group, which can optionally be substi- tuted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
R10 and R11 are independently of each other a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; R12, R13 and R14 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR65-, -SiR70R71-, -POR72-, -CR63=CR64-, or -C≡C-, E is -OR69, -SR69, -NR65R66, -COR68, -COOR67, -CONR65R66, -CN, or F,
G is E, or a d-dsalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by F, Ci-Ci8alkyl, or C-i-C-isalkyl, which is substituted by F and/or interrupted by O; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, Ci-Cisalkyl, - Si(R 2')(R 3')(R14'), or Ci-Ci8alkyl which is interrupted by O;
R12' R13' anc| R14' are independently of each other a d-dsalkyl group, which can optionally be interupted by O; a C6-Ci4arylgroup, which can optionally be substituted by d-dsalkyl ; or a C2-Cioheteroaryl group, which can optionally be substituted by d-dsalkyl ;
R63 and R64 are independently of each other H, d-dsaryl; d-dsaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-; R65 and R66 are independently of each other a C6-Cisaryl group; a d-dsaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; a Ci-Cisalkyl group; or a d-dsalkyl group, which is interrupted by -0-; or
R65 and R66 together form a five or six membered ring,
R67 is a Ce-Cisaryl group; a d-dsaryl group, which is substituted by d-dsalkyl, or Ci- dsalkoxy; a d-dsalkyl group; or a d-dsalkyl group, which is interrupted by -0-,
R68 is H; a d-dsaryl group; a d-dsaryl group, which is substituted by d-dsalkyl, or Ci- dealkoxy; a d-dsalkyl group; or a d-dsalkyl group, which is interrupted by -0-,
R69 is a C6-Ciearyl; a d-dsaryl, which is substituted by d-dsalkyl, or d-dsalkoxy; a d- dealkyl group; or a d-dsalkyl group, which is interrupted by -O-,
R70 and R71 are independently of each other a d-dsalkyl group, a d-dsaryl group, or a d-dsaryl group, which is substituted by d-dsalkyl, and
R72 is a d-dsalkyl group, a d-dsaryl group, or a d-dsaryl group, which is substituted by d-dsalkyl, with the proviso that at least one of the substituents R1 and R6 represent a group of formula -(A )0-(A2)p-(A3)q-(A4)rR16 and with the further proviso that R16 is different from H, if o is 0, p is 0, q is 0 and r is 0. T I is preferably a compound of formula
Figure imgf000010_0001
(Γ), wherein
R1, R2, R3, R4, R5, Re, R7 and R8 are independently of each other H, a d-dsalkyl group, which can optionally be substituted by E and or interupted by D; a d-dsaralkyl group, which can optionally be substituted by G, or a group of formula— (A1)0-(A2)p-(A3)q-(A4)rR16, o is 0, or 1 , p is 0, or 1 , q is 0, or 1 , r is 0, or 1 ,
A1, A2, A3 and A4 are independently of each other a d-d4arylen group, which can optionally be substituted by G, or a d-doheteroarylen group, which can optionally be substituted by G;
R16 is H, -NR10R11, or -Si(R12)(R13)(R14), a d-d4aryl group, which can optionally be substi- tuted by G; or a d-doheteroaryl group, which can optionally be substituted by G;
R10 and R11 are independently of each other a d-d4aryl group, which can optionally be substituted by G; or a d-doheteroaryl group, which can optionally be substituted by G; R12, R13 and R14 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR65-, -SiR70R71-, -POR72-, -CR63=CR64-, or -C≡C- ,
E is -OR69, -SR69, -NR65R66, -COR68, -COOR67, -CONR65R66, -CN, or F,
G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by F, Ci-Ci8alkyl, or Ci-Cisalkyl which is substituted by F and/or interrupted by O; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, Ci-Cisalkyl, - Si(R 2')(R 3')(R14'), or Ci-Ci8alkyl which is interrupted by O;
R12' R13' ANC| RI4' are independently of each other a d-dsalkyl group, which can optionally be interupted by O; a C6-Ci4arylgroup, which can optionally be substituted by C-i-C-isalkyl ; or a C2-Cioheteroaryl group, which can optionally be substituted by Ci-Cisalkyl ;
R63 and R64 are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; Ci-Cisalkyl; or C-i-C-isalkyl which is interrupted by -0-;
R65 and R66 are independently of each other a C6-Cisaryl group; a di-deary! which is substituted by Ci-Cisalkyl, or d-dsalkoxy; a Ci-Cisalkyl group; or a d-dsalkyl group, which is interrupted by -0-; or
R65 and R66 together form a five or six membered ring,
R67 is a Ce-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci- Ci8alkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-,
R68 is H; a C6-Cisaryl group; a di-deary! group, which is substituted by Ci-Cisalkyl, or Ci- Ci8alkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-,
R69 is a C6-Ciearyl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci- Ciealkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-,
R70 and R71 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a Ce-Cisaryl group, which is substituted by Ci-Cisalkyl, and
R72 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a di-deary! group, which is substituted by Ci-Cisalkyl, with the proviso that at least one of the substituents R1 , R2, R3, R4, R5, R6, R7 and R8 represent a group of formula -(A1)0-(A2)p-(A3)q-(A4)rR16 and with the further proviso that R16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
Certain compounds of the present invention have high triplet energy and can show, when used as host in combination with phosphorescent emitters, excellent power efficiencies.
The compounds of the present invention may be used for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electrolumi- nescent devices, such as, for example, organic light-emitting diodes (OLEDs).
Accordingly, a further subject of the present invention is directed to an electronic device, comprising a compound according to the present invention. The electronic device is preferably an electroluminescent device. The compounds of formula I can in principal be used in any layer of an EL device, but are preferably used as host, charge transport and/or charge/exciton blocking material. Particularly, the compounds of formula I are used as host material for green, especially blue light emitting phosphorescent emitters.
Hence, a further subject of the present invention is directed to a charge transport layer, comprising a compound of formula I according to the present invention.
A further subject of the present invention is directed to an emitting layer, comprising a com- pound of formula I according to the present invention. In said embodiment a compound of formula I is preferably used as host material in combination with a phosphorescent emitter.
A further subject of the present invention is directed to a charge/exciton blocking layer, comprising a compound of formula I according to the present invention.
D is preferably -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR65-, wherein R65 is Ci-Ci8alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C6-Ci4aryl, such as phenyl, tolyl, naphthyl, or biphenylyl, or C2-C3oheteroaryl, such as, for example, benzimid-
Figure imgf000012_0001
azo[1 ,2-a]benzimidazo-2-yl ( ), carbazolyl, dibenzofuranyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Cioheteroaryl.
E is preferably -OR69; -SR69; -NR65R65; -COR68; -COOR67; -CON RssRss; or -CN; wherein R65, R67, R68 and R69 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-Ci4aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.
G is preferably -OR69; -SR69; -NR65R65; a d-dsalkyl group, a C6-Ci4aryl group, a C6- Ci4aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2- doheteroaryl group, which is substituted by F, or d-C-isalkyl; or -Si(R 2')(R 3')(R14'); wherein R65, R67, R68 and R69 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-Ci4aryl, such as phenyl, tolyl, naphthyl, or biphenylyl; R12', R13' and R14' are independently of each other; a C6-Ci4aryl group, which can optionally be substituted by Ci-Cisalkyl ; or a C2- doheteroaryl group, which can optionally be substituted by Ci-Cisalkyl. A C2-Cioheteroaryl group is for example, benzimidazo[1 ,2-a]benzimidazo-5-yl
Figure imgf000013_0001
( ), benzimidazo[1 ,2-a]benzimidazo-2-yl ( ), ben- zimidazolo[2,1-b][1 ,3]benzothiazolyl, carbazolyl, dibenzofuranyl, which can be unsubstitut- ed or substituted, especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Cioheteroaryl.
A
Figure imgf000013_0002
ferred, wherein R1, R2, R3 and R6 are independently of each other a group of formula— (A )o-(A2)p-(A3)q-(A4)rR16, wherein o, p, q, r, A1 , A2, A3, A4 and R16 as defined above;
c is 0, or 1 ; d is 0, or 1 ; and
Y1 and Y2 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substi- tuted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally be substituted by G, wherein D, E and G are as defined above.
Among the compounds of formula (I) compounds of formula
Figure imgf000013_0003
wherein R1, R2, R3 and R6 are independently of each other a group of formula—(A1), (A3)q-(A4)rR16, wherein o, p, q, r, A1, A2, A3, A4 and R16 as defined above, or below. In ad of formula (I) compounds of formula
Figure imgf000014_0001
are preferred, wherein R3 and R6 are independently of each other a group of formula— (A1)0-(A2)p-(A3)q-(A4)rR16, wherein o, p, q, r, A1, A2, A3, A4 and R16 as defined above; c is 0, or 1 ; d is 0, or 1 ; and
Y1 and Y2 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally rein D, E and G are as de-
fined above. Compounds of formula
Figure imgf000014_0002
(le') are more preferred, wherein R3 and R6 are independently of each other a group of formula— (A1)0-(A2)p-(A3)q- (A4)rR16, wherein o, p, q, r, A1, A2, A3, A4 and R16 as defined above, or below.
For the group of formula— (A1)0-(A2)p-(A3)q-(A4)rR16 the following preferences apply.
A1, A2, A3 and A4 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, or a C2-C3oheteroarylen group, which can optionally be substituted by G. The C6-C24arylen groups A1, A2, A3 and A4 which optionally can be substituted by G, are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1- naphthylene, or 2-naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9- fluorenylene, phenanthrylene, or anthrylene, which may be unsubstituted or substituted. The C2-C3oheteroarylen groups A1, A2, A3 and A4, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated-electrons such as, for example, benzofu- idylene
Figure imgf000014_0003
), pyrido[2,3-b]indolylene ( ), benzofuro[2,3-
Figure imgf000015_0001
c]pyridylene ( ), benzothiopheno[2,3-c]pyridylene
Figure imgf000015_0002
), pyrido[2,3-c]indolylene ( ), furo[3,2-b:4,5-
Figure imgf000015_0003
b']dipyridylene ( ), thieno[3,2-b:4,5-b']dipy
Figure imgf000015_0004
( ), pyrrolo[3,2-b:4,5-b']dipyridylene ( ), thienylene, benzothiophenylene, thianthrenylene, furylene, furfurylene, 2H-pyranylene,
Figure imgf000015_0005
benzofuranylene, isobenzofuranylene, dibenzofuranylene ( ), diben-
Figure imgf000015_0006
zothiophenylene ( ), phenoxythienylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazi- nylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinolylene, isochinolylene, phthalazinylene, naphthyridinylene, chinoxalinylene, chinazoli- nylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, iso- thiazolylene, phenothiazinylene, isoxazolylene, furazanylene, carbazolylene
), benzimidazo[1 ,2-a]benzimidazo-2,5-ylene
Figure imgf000015_0007
( phenoxazinylene, which can be unsubstituted or substituted. Preferred C6-C24arylen groups are 1 ,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted, especially by C6-Cioaryl, C6-Cioaryl which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl. Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, especially benzofuro[2,3-b]pyridylene, benzothiopheno[2,3-b]pyridylene , pyrido[2,3-b]indolylene , benzofuro[2,3-c]pyridylene, benzothiopheno[2,3-c]pyridylene , pyrido[2,3-c]indolylene fu- ro[3,2-b:4,5-b']dipyridylene, thieno[3,2-b:4,5-b']dipyridylene, pyrrolo[3,2-b:4,5- b']dipyridylene, dibenzofuranylene, dibenzothiophenylene , carbazolylene and benzimid- azo[1 ,2-a]benzimidazo-2,5-ylene , which can be unsubstituted or substituted, especially by C6-Ci4aryl, C6-Ci4aryl which is substituted by Ci-C4alkyl; or C2-Cioheteroaryl.
The C6-C24arylen and C2-C3oheteroarylen groups may be substituted by G.
G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3, a C6-Ci4aryl group, a C6-Ci4aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2-Cioheteroaryl group, which is substituted by F, or Ci-Cisalkyl. Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Cioheteroaryl group. Phenyl, 1-naphthyl and 2- naphthyl are examples of a C6-Ci4aryl group.
Preferably, A1, A2, A3 and A4 are independently of each other a group of the formula
Figure imgf000016_0001
Figure imgf000017_0001
or ; wherein
X is O, S, or NR24
R24 is a C6-C24aryl group, which can optionally be substituted by G, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined above.
R16 may be a C6-C24aryl group, which can optionally be substituted by G, or a C2- C3oheteroaryl group, which can optionally be substituted by G.
The C6-C24aryl group, which optionally can be substituted by G, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted.
The C2-C3oheteroaryl group R16, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as 9H-pyrido[2,3-b]indolyl, benzofuro[2,3- bjpyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyrrolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrol- yl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, in- dolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothia- zolyl, phenothiazinyl, isoxazolyl, furazanyl, benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimid- azo[1 ,2-a]benzimidazo-2-yl, benzimidazolo[2,1-b][1 ,3]benzothiazolyl, carbazolyl, or phe- noxazinyl, which can be unsubstituted or substituted.
The C6-C24aryl and C2-C3oheteroaryl groups may be substituted by G. G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl; -CF3, a C6-C-i4aryl group, a C6-Ci4aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2-Cioheteroaryl group, which is substituted by F, or Ci-Cisalkyl.
Prefered C2-C3oheteroaryl groups are pyridyl, triazinyl, pyrimidinyl, especially 9H-pyrido[2,3- b]indolyl, benzofuro[2,3-b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyr- rolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, benzimi azo-5-yl
Figure imgf000018_0001
( ), benzimidazo[1 ,2-a]benzimidazo-2-yl ( ; R" is
C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl), benzimid-
Figure imgf000018_0002
azolo[2,1-b][1 ,3]benzothiazolyl ( , or ), carbazolyl, dibenzofuranyl, and dibenzothiophenyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl.
R16 is preferably H, or a group of the formula -Si(R12)(R13)(R14),
Figure imgf000018_0003
Figure imgf000019_0001
, wherein
R12, R13 and R14 are independently of each other a phenyl group, which can optionally be substituted by one, or more Ci-Cisalkyl groups;
R21 and R21 ' are independently of each other H, a phenyl group, or a Ci-Cisalkyl group;
Figure imgf000019_0002
X is O, S, or NR24,
R24 is a C6-C24aryl group, which can optionally be substituted by G, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined above.
Compounds of formula (I) are especially preferred, wherein
o is 0, or 1 , p is 0, or 1 , q is 0, or 1 , r is 0, or 1 , A1, A2, A3 and A4 are independently of each oth
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000021_0001
is , or , with the proviso that R16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
Figure imgf000022_0001
22
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001

Figure imgf000026_0001

Figure imgf000027_0001

Figure imgf000028_0001
Figure imgf000029_0001
e), (XVIf);
Figure imgf000030_0001
If),
Figure imgf000031_0001
(XVIII), 31
Figure imgf000032_0001
5
Figure imgf000033_0001
In another preferred embodiment the group of the formula -(A1)0-(A2)p-(A3)q-(A4)rR16 is a
Figure imgf000034_0001
ĨXVIIIf),
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000036_0002
Figure imgf000036_0003
More preferred, the group of the formula -(A1)0-(A2)p-(A3)q-(A4)rR16 is a group of formula (Xlla), (Xllb), (Xllc), (Xllt), (Xlllb), (Xlllh), (Xllli), (Xlllj), (XlVb), (XIVc), (XIVo), (XIVp), (XlVq), (XIVo), (XIVp), (XlVq), (XIVz), (XVc), (XVd), (XVh), (XVI), (XVo), (XVq), (XVIc), (XVIe), (XVIf); (XVIIa), (XVIIe), (XVIIf), or (XVIIs). In a preferred embodiment the present invention is directed to compounds of formula
e
Figure imgf000037_0001
Figure imgf000037_0002
group of formula -(A1)0-
(A2)p-(A3)q-(A4)rR16.
rou of formula -A1 -A2 -A3 -A4 R followin references a ly:
and R16
Figure imgf000037_0003
is or
Figure imgf000038_0001
Figure imgf000039_0001
Above alternatives i), ii) and iv) are preferred.
In another embodiment of the present invention the following preference applies for the group of formula -(AV(A2)P-(A3)q- 4)rR16:
v , and R16 is Si(Ph)3,
Figure imgf000039_0002
In a particularly preferred embodiment the present invention is directed to compounds of formula
Figure imgf000039_0003
wherein R1, R2, R3 and R6 are a group of formula -(A )0-(A2)p-(A3)q-(A4)rR16 , wherein
Figure imgf000040_0001
40
Figure imgf000041_0001
Figure imgf000042_0001
In another particularly preferred embodiment the present invention is directed to compounds of formula (la'), (lb'), (Ic'), or (Id'), wherein R1 , R2, R3 and R6 are a group of formula -(Ai)o-(A2)p-(A3)q-(A4)rRi6 , wherein -(Ai)0-(A2)P-(A3)q-(A4)r is a single bond, or a group of
Figure imgf000043_0001
In compounds of formula (le') R3 and R6 may be the same or different.
In another particularly preferred embodiment the present invention is directed to compounds of formula (le'), wherein R3 and R6 are the same, or different from each other and are a group of formula -(Ai)0-(A2) -(A3) -(A4)rRi6, wherein -(Ai)0-(A2) -(A3) -(A4)r is a sin-
Figure imgf000043_0002
Examples of preferred compounds are shown in the tables below:
Figure imgf000043_0003
Compound L R16
A-1
- cH 3
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
C-17
C-18
C-19
C-20
C-21
C-22
C-23
„
C-24 o
C-25
C-26
Figure imgf000054_0001
N
Compound L R16
D-1
-
D-2
-
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
E-4
E-5
E-6
E-7
E-8
E-9 
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
63
Figure imgf000064_0001
e used as host
Figure imgf000065_0001
Halogen is fluorine, chlorine, bromine and iodine.
Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1 ,1 ,3,3,5,5- hexa methyl hexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl. d-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2- ethylhexyl. Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl.
Ci-C25alkoxy groups (Ci-Cisalkoxy groups) are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un- decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of d-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2- dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1 ,1 ,3,3-tetramethylbutoxy and 2- ethylhexyloxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy. The term "cycloalkyl group" is typically C5-Ci2cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
C6-C24aryl (C6-Cisaryl), which optionally can be substituted, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted. Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-Cioaryl group.
C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, co-phenyl-butyl, ω,ω-dimethyl- o-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, co-phenyl-eicosyl or ω-phenyl-docosyl, preferably Cz-Cisaralkyl such as benzyl, 2-benzyl-2- propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, co-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, co-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C7-Ci2aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-co-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2- phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.
C2-C3oheteroaryl represents a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzo- furanyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phe- nanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, 4-imidazo[1 ,2-a]benzimidazoyl, 5-benzimidazo[1 ,2-a]benzimidazoyl, benzimidazolo[2,1-b][1 ,3]benzothiazolyl, carbazolyl, or phenoxazinyl, which can be unsubstituted or substituted. Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2- a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Ci4heteroaryl group.
C6-C24arylen groups, which optionally can be substituted by G, are typically phenylene, 4- methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene, or 2- naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenan- thrylene, or anthrylene, which may be unsubstituted or substituted. Preferred C6-C24arylen groups are 1 ,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted.
C2-C3oheteroarylen groups, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated -electrons such as thienylene, benzothiophenylene, dibenzothio- phenylene, thianthrenylene, furylene, furfurylene, 2H-pyranylene, benzofuranylene, isoben- zofuranylene, dibenzofuranylene, phenoxythienylene, pyrrolylene, imidazolylene, pyrazol- ylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinol- ylene, isochinolylene, phthalazinylene, naphthyridinylene, chinoxalinylene, chinazolinylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenan- thridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, isothiazol- ylene, phenothiazinylene, isoxazolylene, furazanylene, carbazolylene, benzimidazo[1 ,2- a]benzimidazo-2,5-ylene, or phenoxazinylene, which can be unsubstituted or substituted. Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolylene, dibenzofuranylene and benzimidazo[1 ,2-a]benzimidazo-2,5-ylene
Figure imgf000067_0001
( ), which can be unsubstituted or substituted, especially by C6-Cioaryl,
C6-Cioaryl which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl.
Possible substituents of the above-mentioned groups are d-dalkyl, a hydroxyl group, a mercapto group, d-dalkoxy, d-dalkylthio, halogen, halo-d-dalkyl, or a cyano group. The C6-C24aryl (d-dsaryl) and d-doheteroaryl groups are preferably substituted by one, or more d-dalkyl groups.
If a substituent occurs more than one time in a group, it can be different in each occurrence.
Halo-d-dalkyl is an alkyl group where at least one of the hydrogen atoms is replaced by a halogen atom. Examples are -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, and -C(CF3)3.
The wording "substituted by G" means that one, or more, especially one to three substituents G might be present.
As described above, the aforementioned groups may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of groups containing at least 2 carbon atoms connected to one another by single bonds; d-dsaryl is not interrupted; interrupted arylalkyl contains the unit D in the alkyl moiety, d-dsalkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (Ch Ch O i-g- Rx, where R* is H or d-doalkyl or d-doalkanoyl (e.g. CO-CH(dH5)dH9), CH2-CH(ORy')- CH2-0-Ry, where Ry is d-dsalkyl, d-Ci2cycloalkyl, phenyl, C7-d5phenylalkyl, and Ry' embraces the same definitions as Ry or is H ;
d-dalkylene-COO-Rz, e.g. CH2COORz, CH(CH3)COORz, C(CH3)2COORz, where Rz is H , d-dsalkyl, (CH2CH20)i-9-Rx, and Rx embraces the definitions indicated above;
CH2CH2-0-CO-CH=CH2; CH2CH(OH)CH2-0-CO-C(CH3)=CH2. An alkyl group substituted by E is, for example, an alkyl group where at least one of the hydrogen atoms is replaced by F. Examples are -CF3, -CF2CF3,
-CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, and -C(CF3)3.
Figure imgf000068_0001
The synthesis of is described, for example, in Achour, Reddouane;
Zniber, Rachid, Bulletin des Societes Chimiques Beiges 96 (1987) 787-92.
Figure imgf000068_0002
uitable base skeletons of the formula are either commercially available
(especially in the cases when X is S, O, NH), or can be obtained by processes known to those skilled in the art. Reference is made to WO2010079051 and EP 1885818.
The halogenation can be performed by methods known to those skilled in the art. Preference is given to brominating or iodinating in the 3 and 6 positions (dibromination) or in the 3 or 6 positions (monobromination) of the base skeleton of the formula 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole).
Optionally substituted dibenzofurans, dibenzothiophenes and carbazoles can be dibromin- ated in the 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) with bromine or NBS in glacial acetic acid or in chloroform. For example, the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0°C. Suitable processes are described, for example, in M. Park, J.R. Buck, C.J. Rizzo, Tetrahedron, 54 (1998) 12707-12714 for X= NPh, and in W. Yang et al., J. Mater. Chem. 13 (2003) 1351 for X= S. In addition, 3,6-dibromocarbazole, 3,6-dibromo-9-phenylcarbazole, 2,8- dibromodibenzothiophene, 2,8-dibromodibenzofuran, 2-bromocarbazole, 3- bromodibenzothiophene, 3-bromodibenzofuran, 3-bromocarbazole, 2- bromodibenzothiophene and 2-bromodibenzofuran are commercially available.
Monobromination in the 4 position of dibenzofuran (and analogously for dibenzothiophene) is described, for example, in J. Am. Chem. Soc. 1984, 106, 7150. Dibenzofuran (diben- zothiophene) can be monobrominated in the 3 position by a sequence known to those skilled in the art, comprising a nitration, reduction and subsequent Sandmeyer reaction.
Monobromination in the 2 position of dibenzofuran or dibenzothiophene and monobromina- tion in the 3 position of carbazole are effected analogously to the dibromination, with the exception that only one equivalent of bromine or NBS is added.
Alternatively, it is also possible to utilize iodinated dibenzofurans, dibenzothiophenes and carbazoles. The preparation is described, inter alia, in Tetrahedron. Lett. 47 (2006) 6957- 6960, Eur. J. Inorg. Chem. 24 (2005) 4976-4984, J. Heterocyclic Chem. 39 (2002) 933-941 , J. Am. Chem. Soc. 124 (2002) 11900-11907, J. Heterocyclic Chem, 38 (2001) 77-87.
For the nucleophilic substitution, CI- or F-substituted dibenzofurans, dibenzothiophenes and carbazoles are required. The chlorination is described, inter alia, in J. Heterocyclic Chemistry, 34 (1997) 891-900, Org. Lett., 6 (2004) 3501-3504; J. Chem. Soc. [Section] C: Organic, 16 (1971) 2775-7, Tetrahedron Lett. 25 (1984) 5363-6, J. Org. Chem. 69 (2004) 8177-8182. The fluorination is described in J. Org. Chem. 63 (1998) 878-880 and J. Chem. Soc, Perkin Trans. 2, 5 (2002) 953-957.
The introduction of the group
Figure imgf000069_0001
performed in the presence of a base.
Suitable bases are known to those skilled in the art and are preferably selected from the group consisting of alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2, alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH2, alkali metal or alkaline earth metal carbonates such as K2CO3 or CS2CO3, and alkali metal alkox- ides such as NaOMe, NaOEt. In addition, mixtures of the aforementioned bases are suitable. Particular preference is given to NaOH, KOH, NaH or K2CO3.
Heteroarylation can be affected, for example, by copper-catalyzed coupling of
Figure imgf000069_0002
(Ullmann reaction).
The N-arylation is, for example, disclosed in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001 ) 181 - 186 and Eur. J. Org. Chem. (2007) 2147-2151. The reaction can be performed in solvent or in a melt. Suitable solvents are, for example, (polar) aprotic solvents such as dimethyl sulfoxide, dimethylfor- mamide, N-methyl-2-pyrrolidone (NMP), tridecane or alcohols.
Figure imgf000070_0001
The synthesis of 9-(8-bromodibenzofuran-2-yl)carbazole, , is
2010079051. The synthesis of 2-bromo-8-iodo-dibenzofurane,
Figure imgf000070_0002
is described in EP 1885818.
Figure imgf000070_0003
A possible synthesis route for the compound of formula is shown in the following scheme:
Figure imgf000070_0004
Reference is made to Angew. Chem. Int. Ed. 46 (2007)1627-1629 and Synthesis 20 (2009) 3493.
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and car- bazoles can be readily prepared by an increasing number of routes. An overview of the synthetic routes is, for example, given in Angew. Chem. Int. Ed. 48 (2009) 9240 - 9261. By one common route diboronic acid or diboronate group containing dibenzofurans, diben- zothiophenes, and carbazoles can be obtained by reactin
dibenzothiophenes and carbazoles with (Y10)2B-B(OY1)2
Figure imgf000071_0001
or Y B- Y in the presence of a catalyst, such as, for example, [1 ,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), complex (Pd(CI)2(dppf)), and a base, such as, for example, potassium acetate, in a solvent, such as, for example, dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene (cf. Prasad Appukkuttan et al., Syn- lett 8 (2003) 1204), wherein Y1 is independently in each occurrence a Ci-Ci8alkylgroup and Y2 is independently in each occurrence a C2-Cioalkylene group, such as -CY3Y4-CY5Y6-, or -CY7Y8-CY9Y10- CY Y12-, wherein Y3, Y4, Ys, γβ, γ?, γβ_ γθ γιο. γιι and Υ12 are independently of each other hydrogen, or a Ci-Ci8alkylgroup, especially -C(CH3)2C(CH3)2-, - C(CH3)2CH2C(CH3)2-, or -CH2C(CH3)2CH2-, and Y13 and Y14 are independently of each other hydrogen, or a Ci-Ci8alkylgroup.
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with alkyl lithium reagents, such as, for example, n-butyl lithium, or t-buthyl lithium, followed nic esters, such as, for example, B(isopropoxy)3,
B(methoxy)3, or
Figure imgf000071_0002
(cf. Synthesis (2000) 442-446).
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting dibenzofurans, dibenzothiophenes and carbazoles with lithium amides, such as, for example, lithium diisopropylamide (LDA) followed by esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
Figure imgf000071_0003
(J. Org. Chem. 73 (2008) 2176-2181). Diboronic acid or diboronate gr nzothiophenes and car-
bazoles, such as, for example,
Figure imgf000071_0004
, can be reacted with equimolar amounts of halogenated dibenzofurans, dibenzothiophenes, carbazoles and 4H-
Figure imgf000072_0001
imidazo[1 ,2-a]imidazoles, such as, for example and
Figure imgf000072_0002
, in a solvent and in the presence of a catalyst. The catalyst may be one of the μ-halo(triisopropylphosphine)(η3-allyl)palladium(ll) type (see for example W099/47474).
Preferably, the Suzuki reaction is carried out in the presence of an organic solvent, such as an aromatic hydrocarbon or a usual polar organic solvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixtures thereof, most preferred toluene. Usually, the amount of the solvent is chosen in the range of from 1 to 10 I per mol of boronic acid derivative. Also preferred, the reaction is carried out under an inert atmosphere such as nitrogen, or argon. Further, it is preferred to carry out the reaction in the presence of an aqueous base, such as an alkali metal hydroxide or carbonate such as NaOH, KOH, Na2C03, K2CO3, Cs2C03 and the like, preferably an aqueous K2CO3 solution is chosen. Usually, the molar ratio of the base to boronic acid or boronic ester derivative is chosen in the range of from 0.5:1 to 50:1 , very especially 1 :1. Generally, the reaction temperature is chosen in the range of from 40 to 180°C, preferably under reflux conditions. Preferred, the reaction time is chosen in the range of from 1 to 80 hours, more preferably from 20 to 72 hours. In a preferred embodiment a usual catalyst for coupling reactions or for polycondensation reactions is used, preferably Pd-based, which is described in WO2007/101820. The palladium compound is added in a ratio of from 1 :10000 to 1 :50, preferably from 1 :5000 to 1 :200, based on the number of bonds to be closed. Preference is given, for example, to the use of palla- dium(ll) salts such as PdAc2 or Pd2dba3 d from the
Figure imgf000072_0003
group consisting of wherein cy - - . The ligand is added in a ratio of from 1 : 1 to 1 :10, based on Pd. Also preferred, the catalyst is added as in solution or suspension. Preferably, an appropriate organic solvent such as the ones described above, preferably benzene, toluene, xylene, THF, dioxane, more preferably toluene, or mixtures thereof, is used. The amount of solvent usually is chosen in the range of from 1 to 10 I per mol of boronic acid derivative. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Lead- beater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, G. Wegner in Macromol. Rap- id Commun. 17 (1996) 239-252 and G. A. Molander und B. Canturk, Angew. Chem. , 121 (2009) 9404 - 9425.
The synthesis of aza- and diaza-dibenzofuran is known in the literature, or can be done in analogy to known procedures.
JP2011084531 describes, for example, the synthesis of benzofuro[3,2-b]pyridine in two steps starting from 2-bromopyridin-3-ol using a base catalyzed cyclisation. The brominated ation with bromine in the presence of silver sulfate.
Figure imgf000073_0001
US2010/0187984 describes, for example, the synthesis of 3,6-dichloro-benzofuro[2,3- b]pyridine in three steps starting from 2-amino-5-chloropyridine using a cyclisation of a dia- zoniumion salt.
Figure imgf000073_0002
L. Kaczmarek, Polish Journal of Chemistry 59 (1985) 1141 describes the synthesis of fu- ro[3,2-b:4,5-b]dipyridine starting from 2-(3-amino-2-pyridyl)pyridin-3-amine using an acid catalyzed cyclisation of a diazoniumion salt.
Figure imgf000074_0001
JP2002284862 describes the syntheses of 2,7-dibromo-furo[3,2-b:4,5-b]dipyridine starting from 2-(3-amino-5-bromo-2-pyridyl)-5-bromo-pyridin-3-amine using an acid catalyzed cy- clisation of a diazoniumion salt. The synthesis of the starting material is described by Y. F
Figure imgf000074_0002
J. Liu, J. Org. Chem. 73, 2951 (2008) describes e.g. the synthesis of benzofuro[2,3- c]pyridine using a copper catalyzed cyclisation step.
Figure imgf000074_0003
The synthesis of benzimidazolo[2,1-b][1 ,3]benzothiazole is, for example, described by Z. Wu et al., Eur. J. Org. Chem. (201 1) 5242-5245:
Figure imgf000074_0004
The halogenation can be performed by methods known to those skilled in the art. 4-lodobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting enzimidazo- lo[2,1-b][1 ,3]benzothiazole with butyl lithium and I2 in tetra arylation can
Figure imgf000074_0005
be effected, for example, by copper-catalyzed coupling of , or
Figure imgf000074_0006
to 4-iodobenzimidazolo[2,1-b][1 ,3]benzothiazole (Ullmann reaction). 4-Chlorobenzimidazolo[2,1-b][1 ,3]benzothiazole can be prepared as described in Organic &
Figure imgf000075_0001
2-lodobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting benzimidazo- lo[2,1-b][1 ,3]benzothiazole in CH3COOH and CF3COOH in the presence of N- iodosuccinimide (NIS).
Figure imgf000075_0002
2-Bromobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting 2- mercaptobenzimidazole and 1 ,4-dibromo-2-nitro-benzene in the presence of caesiu bonate in DMSO (dimethyl sulfoxide).
Figure imgf000075_0003
2-Bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting 2- bromobenzimidazolo[2,1-b][1 ,3]benzothiazole with N-iodosuccinimide (NIS) in acetic acid in the presence of trifluoroacetic acid,
Figure imgf000075_0004
A possible synthesis route for compound F-2 is shown below:
Figure imgf000075_0005
Reference is made to Example 5 of the present application.
9-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting 9-iodobenzimidazolo[2,1-b][1 ,3]benzothiazole
bis(pinacolato)doboran in DMF using potassium acetate as base and [Pd(dppf)Cl2] as catalyst (Chem. Eur. J. 10 (2004) 2681-2688). bis(pinacolato)diboron,
Figure imgf000076_0001
9-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole can
be reacted with a compound Suzuki con
ditions to a compound of form
Figure imgf000076_0002
(D-14). The above compound can also be prepared by Suzuki coupling of 9- iodobenzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[8-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole (WO2012130709).
Figure imgf000076_0003
A possible synthesis route for compound B-3 is shown below:
Figure imgf000076_0004
Alternatively, compounds of formula I can be obtained by reacting a compound of formula X with 1 ,3-dihydrobenzimidazole-2-thione in the presence of a base, such as, for example, CS2CO3, in a solvent, such as, for example, dimethylsulfoxide, at elevated temperatures, especially 130 to 170 °C.
Figure imgf000077_0001
Figure imgf000077_0002
. Reference is made to Examples 1 to 3. It has been found that the compounds of the formula I are particularly suitable for use in applications in which charge carrier conductivity is required, especially for use in organic electronics applications, for example selected from switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs), the compounds of the formula I being particularly suitable in OLEDs for use as matrix material in a light-emitting layer and/or as electron and/or exciton blocker material and/or as hole and/or exciton blocker material, especially in combination with a phosphorescence emitter. In the case of use of the inventive compounds of the formula I in OLEDs, OLEDs which have good efficiencies and a long lifetime and which can be operated especially at a low use and operating voltage are obtained. The inventive compounds of the formula I are suitable especially for use as matrix and/or charge/exciton blocker materials for blue and green emitters, for example light blue or deep blue emitters, these being especially phosphorescence emitters. Furthermore, the compounds of the formula I can be used as conductor/complementary materials in organic electronics applications selected from switching elements and organic solar cells. The compounds of the formula I can be used as matrix material and/or charge/exciton blocker material and/or charge transport material (charge conductor material). The inventive compounds of the formula I are preferably used as matrix materials in organic electronics applications, especially in OLEDs.
In the emission layer or one of the emission layers of an OLED, it is also possible to combine an emitter material with a matrix material of the compound of the formula I and a further matrix material which has, for example, a good hole transport property. This achieves a high quantum efficiency of this emission layer.
When a compound of the formula I is used as matrix (host) material in an emission layer and additionally as charge/exciton blocker material, owing to the chemical identity or similarity of the materials, an improved interface between the emission layer and the adjacent charge/exciton blocker material, which can lead to a decrease in the voltage with equal luminance and to an extension of the lifetime of the OLED. Moreover, the use of the same material for charge/exciton blocker material and for the matrix of an emission layer allows the production process of an OLED to be simplified, since the same source can be used for the vapor deposition process of the material of one of the compounds of the formula I. Suitable structures of organic electronic devices are known to those skilled in the art and are specified below.
The organic transistor generally includes a semiconductor layer formed from an organic layer with charge transport capacity; a gate electrode formed from a conductive layer; and an insulat- ing layer introduced between the semiconductor layer and the conductive layer. A source electrode and a drain electrode are mounted on this arrangement in order thus to produce the transistor element. In addition, further layers known to those skilled in the art may be present in the organic transistor. The organic solar cell (photoelectric conversion element) generally comprises an organic layer present between two plate-type electrodes arranged in parallel. The organic layer may be configured on a comb-type electrode. There is no particular restriction regarding the site of the organic layer and there is no particular restriction regarding the material of the electrodes. When, however, plate-type electrodes arranged in parallel are used, at least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed from two sublayers, i.e. a layer with p-type semiconductor properties or hole transport capacity, and a layer formed with n-type semiconductor properties or charge transport capacity. In addition, it is possible for further layers known to those skilled in the art to be present in the organic solar cell. The layers with charge transport capacity may com- prise the compounds of formula I.
It is likewise possible that the compounds of the formula I are present both in the light- emitting layer (preferably as matrix material) and in the blocking layers (as charge/exciton blockers). The present invention further provides an organic light-emitting diode comprising an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i), and if appropriate at least one further layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for elec- trons/excitons, at least one hole injection layer, at least one hole transport layer, at least one electron injection layer and at least one electron transport layer, wherein the at least one compound of the formula I is present in the light-emitting layer (e) and/or in at least one of the further layers. The at least one compound of the formula I is preferably present in the light-emitting layer and/or the charge/exciton blocking layers.
In a preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of the formula la, lb, Ic, Id, or le, very especially la', lb', Ic', Id', or le', is used as charge transport material. Examples of preferred compounds of formula I are compounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G-1 to E-20 shown above.
In another preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of the formula la, lb, Ic, Id, or le, very especially la', lb', Ic', Id', or le', is used as charge/exciton blocker material. Examples of preferred compounds of formula I are compounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G-1 to E-20 shown above.
The present application further relates to a light-emitting layer comprising at least one compound of the formula I.
Structure of the inventive OLED
The inventive organic light-emitting diode (OLED) thus generally has the following structure:
an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i).
The inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:
1. Anode (a)
2. Hole transport layer (c)
3. Light-emitting layer (e)
4. Blocking layer for holes/excitons (f)
5. Electron transport layer (g)
6. Cathode (i)
Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art. For example, it is possible that the OLED does not have all of the layers mentioned; for example, an OLED with layers (a) (anode), (e) (light-emitting layer) and (i) (cathode) is likewise suitable, in which case the functions of the layers (c) (hole transport layer) and (f) (blocking layer for holes/excitons) and (g) (electron transport layer) are assumed by the adjacent layers. OLEDs which have layers (a), (c), (e) and (i), or layers (a), (e), (f), (g) and (i), are likewise suitable. In addition, the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light- emitting layer (e).
It is additionally possible that a plurality of the aforementioned functions (electron/exciton blocker, hole/exciton blocker, hole injection, hole conduction, electron injection, electron conduction) are combined in one layer and are assumed, for example, by a single material present in this layer. For example, a material used in the hole transport layer, in one embodiment, may simultaneously block excitons and/or electrons.
Furthermore, the individual layers of the OLED among those specified above may in turn be formed from two or more layers. For example, the hole transport layer may be formed from a layer into which holes are injected from the electrode, and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer. The electron conduction layer may likewise consist of a plurality of layers, for example a layer in which electrons are injected by the electrode, and a layer which receives electrons from the electron injection layer and transports them into the light-emitting layer. These layers mentioned are each selected according to factors such as energy level, thermal resistance and charge carrier mobility, and also energy difference of the layers specified with the organic layers or the metal electrodes. The person skilled in the art is capable of selecting the structure of the OLEDs such that it is matched optimally to the organic compounds used in accordance with the invention.
In a preferred embodiment the OLED according to the present invention comprises in this order:
(a) an anode,
(b) optionally a hole injection layer,
(c) optionally a hole transport layer,
(d) optionally an exciton blocking layer
(e) an emitting layer,
(f) optionally a hole/ exciton blocking layer
(g) optionally an electron transport layer,
(h) optionally an electron injection layer, and
(i) a cathode.
In a particularly preferred embodiment the OLED according to the present invention comprises in this order:
(a) an anode,
(b) optionally a hole injection layer,
(c) a hole transport layer,
(d) an exciton blocking layer
(e) an emitting layer,
(f) a hole/ exciton blocking layer (g) an electron transport layer, and
(h) optionally an electron injection layer, and
(i) a cathode. The properties and functions of these various layers, as well as example materials are known from the prior art and are described in more detail below on basis of preferred embodiments.
Anode (a):
The anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 11 , 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (a) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (June 11 , 1992). Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. Anode (and substrate) may be sufficiently transparent to create a bottom-emitting device. A preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate). A reflective anode may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed. Other anode materials and structures may be used.
Hole injection layer (b):
Generally, injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or a charge generating layer, into an adjacent organic layer. Injection layers may also perform a charge transport function. The hole injection layer may be any layer that improves the injection of holes from anode into an adjacent organic layer. A hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, or it may be a vapor deposited small molecule material, such as, for example, CuPc or MTDATA. Polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS.
Hole transport layer (c):
Either hole-transporting molecules or polymers may be used as the hole transport material. Suitable hole transport materials for layer (c) of the inventive OLED are disclosed, for ex- ample, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996, US20070278938, US2008/0106190, US201 1/0163302 (triarylamines with (di)benzothiophen/(di)benzofuran; Nan-Xing Hu et al. Synth. Met. 1 11 (2000) 421 (in- dolocarbazoles), WO2010002850 (substituted phenylamine compounds) and
WO2012/16601 (in particular the hole transport materials mentioned on pages 16 and 17 of WO2012/16601). Combination of different hole transport material may be used. Reference
is m (HTL1-1)
and
Figure imgf000082_0001
(HTL2-1) constitute the hole transport layer.
Customarily used hole-transporting molecule sisting of
Figure imgf000082_0002
(4-phenyl-N-(4-p -[4-(4-phenyl-
phenyl)phenyl]anilino)phenyl]phenyl]aniline),
Figure imgf000082_0003
(4-phenyl-N-(4- (4-phenyl-N-(4-phenylphenyl)anilino)phenyl]phenyl]aniline),
Figure imgf000082_0004
(4-phenyl-N-[4-(9-phenylcarbazol-3-yl)phenyl]-N-(4- phenylphenyl)aniline), odiazasilole-
2,2'-3a,7a-dihydro-1 ,3,2
Figure imgf000083_0001
-benzodiazasilole]),
(N2,N2,N2',N2',N7,N7,N7',N7'-octakis(p^ 4,4'- bis[N-(1-naphthyl)-N-phenylamino]biphenyl (a-NPD), N,N'-diphenyl-N,N'-bis(3- methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine (TPD), 1 ,1-bis[(di-4-tolylamino)phenyl]- cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1 ,1 '-(3,3'-dimethyl)- biphenyl]-4,4'-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA), a-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphe- nylhydrazone (DEH), triphenylamine (TPA), bis[4-(N,N-diethylamino)2-methylphenyl](4- methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]5-[p-
(diethylamino)phenyl]pyrazoline (PPR or DEASP), 1 ,2-trans-bis(9H-carbazol9-yl)- cyclobutane (DCZB), N,N,N',N'-tetrakis(4-methylphenyl)-(1 ,1 '-biphenyl)-4,4'-diamine (TTB), fluorine compounds such as 2,2',7,7'-tetra(N,N-di-tolyl)amino9,9-spirobifluorene (spiro- TTB), N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)9,9-spirobifluorene (spiro-NPB) and 9,9- bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9Hfluorene, benzidine compounds such as Ν,Ν'- bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine and porphyrin compounds such as copper phthalocyanines. In addition, polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PE- DOT/PSS.
In a preferred embodiment it is possible to use metal carbene complexes as hole transport materials. Suitable carbene complexes are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418 A2, WO2005/1 13704, WO2007/115970,
WO2007/1 15981 and WO20 example of a suitable carbene complex is
lr(DPBIC)3 with the formula:
Figure imgf000083_0002
The hole-transporting layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 2003, 4495 and Pfeiffer et al., Organic Electronics 2003, 4, 89 - 103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For ex- ample it is possible to use mixtures in the hole-transporting layer, in particular mixtures which lead to electrical p-doping of the hole-transporting layer. p-Doping is achieved by the addition of oxidizing materials. These mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example M0O2, M0O3, WOx, ReCb and/or V2O5, preferably M0O3 and/or ReCb, more pref- erably M0O3, or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6- tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8- tetracyanoquinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 1 1 ,11 ,12,12- tetracyanonaphtho2,6-quinodimethane, 2-fluoro-7,7,8,8-tetracyanoquino-dimethane, 2,5- difluoro-7,7,8,8etracyanoquinodimethane, dicyanomethylene-1 ,3,4,5,7,8-hexafluoro-6H- naphthalen-2-ylidene)malononitrile (Fe-ΤΝΑΡ), Mo(tfd)3 (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35), 12530-12531 ), compounds as described in EP1988587,
US2008265216, EP2180029, US20100102709, WO2010132236, EP2180029 and quinone compounds as mentioned in EP2401254. Preferred mixtures comprise the aforementioned carbene complexes, such as, for example, the carbene complex HTM-1 , and M0O3 and/or ReCb, especially M0O3. In a particularly preferred embodiment the hole transport layer comprises from 0.1 to 10 wt % of M0O3 and 90 to 99.9 wt % carbene complex, especially of the carbene complex HTM-1 , wherein the total amount of the M0O3 and the carbene com- plex is 100 wt %.
Exciton blocking layer (d):
Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. An electron/exciton blocking layer (d) may be disposed between the first emitting layer (e) and the hole transport layer (c), to block electrons from emitting layer (e) in the direction of hole transport layer (c). Blocking layers may also be used to block excitons from diffusing out of the emissive layer. Suitable metal complexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, W02006/056418 A2, WO2005/113704, WO2007/115970, WO2007/115981 and WO2008/000727. Explicit reference is made here to the disclosure of the WO applications cited, and these disclosures shall be considered to be incorporated into the content of the present application. One example of a suitable carbene complex is compound HTM-1. Emitting layer (e) The light-emitting layer (e) comprises at least one emitter material. In principle, it may be a fluorescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art. The at least one emitter material is preferably a phosphorescence emitter. The phosphorescence emitter compounds used with preference are based on metal com- plexes, and especially the complexes of the metals Ru, Rh, Ir, Pd and Pt, in particular the complexes of Ir, have gained significance. The compounds of the formula I can be used as the matrix in the light-emitting layer.
Suitable metal complexes for use in the inventive OLEDs are described, for example, in documents WO 02/60910 A1 , US 2001/0015432 A1 , US 2001/0019782 A1 ,
US 2002/0055014 A1 , US 2002/0024293 A1 , US 2002/0048689 A1 , EP 1 191 612 A2, EP 1 191 613 A2, EP 1 21 1 257 A2, US 2002/0094453 A1 , WO 02/02714 A2,
WO 00/70655 A2, WO 01/41512 A1 , WO 02/15645 A1 , WO 2005/019373 A2,
WO 2005/113704 A2, WO 2006/1 15301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 2006121811 A1 , WO 2007095118 A2, WO 2007/115970, WO 2007/115981 ,
WO 2008/000727, WO2010129323, WO2010056669, WO10086089, US2011/0057559, WO2011/106344, US201 1/0233528, WO2012/048266 and WO2012/172482.
Further suitable metal complexes are the commercially available metal complexes tris(2- phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C2'), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l-phenylisoquinoline), iridium(lll) bis(2,2'-benzothienyl)pyridinato-N,C3')(acetylacetonate), tris(2-phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-N,C2)picolinate, iridium(lll) bis(1- phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acetylacetonato)iridium(lll), iridium(lll) bis(di-benzo[f,h]quinoxaline)(acetylacetonate), iridium(lll) bis(2-methyldi- benzo[f,h]quinoxaline)(acetylacetonate) and tris(3-methyl-1-phenyl-4-trimethylacetyl-5- pyrazolino)terbium(lll), bis[1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline](acetyl- acetonato)iridium(lll), bis(2-phenylbenzothiazolato)(acetylacetonato)iridium(lll), bis(2-(9,9- dihexylfluorenyl)-1-pyridine)(acetylacetonato)iridium(lll), bis(2-benzo[b]thiophen-2-yl- pyridine)(acetylacetonato)iridium(lll).
In addition, the following commercially available materials are suitable:
tris(dibenzoylacetonato)mono(phenanthroline)europium(lll), tris(dibenzoylmethane)- mono(phenanthroline)europium(lll), tris(dibenzoylmethane)mono(5-aminophenanthroline)- europium(lll), tris(di-2-naphthoylmethane)mono(phenanthroline)europium(lll), tris(4- bromobenzoylmethane)mono(phenanthroline)europium(lll), tris(di(biphenyl)methane)- mono(phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4,7-diphenyl- phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4,7-di-methyl- phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4,7-dimethylphenan- throlinedisulfonic acid)europium(lll) disodium salt, tris[di(4-(2-(2-ethoxyethoxy)ethoxy)- benzoylmethane)]mono(phenanthroline)europium(lll) and tris[di[4-(2-(2-ethoxy- ethoxy)ethoxy)benzoylmethane)]mono(5-aminophenanthroline)europium(lll), osmium(ll) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1 ,2,4-triazolato)diphenylmethylphosphine, os- mium(ll) bis(3-(trifluoromethyl)-5-(2-pyridyl)-1 ,2,4-triazole)dimethylphenylphosphine, osmi- um(ll) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1 ,2,4- triazolato)dimethylphenylphosphine, osmium(ll) bis(3-(trifluoromethyl)-5-(2-pyridyl)- pyrazolato)dimethylphenylphosphine, tris[4,4'-di-tert-butyl(2,2')-bipyridine]ruthenium(lll), osmium(ll) bis(2-(9,9-dibutylfluorenyl)-1-isoquinoline(acetylacetonate). Preferred phosphorescence emitters are carbine complexes. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727, WO2009050281 , WO2009050290, WO2011051404, US2011/057559 WO2011/073149, WO2012/121936A2,
US2012/0305894A1 , WO2012/170571 , WO2012/170461 , WO2012/170463,
WO2006/12181 1 , WO2007/095118, WO2008/156879, WO2008/156879, WO2010/068876, US201 1/0057559, WO2011/106344, US2011/0233528, WO2012/048266 and
WO2012/172482.
Preferably, the light emitting layer (e) comprises at least one carbine complex as phosphorescence emitter. Suitable carbine complexes are, for example, compounds of the
M[carbene]n 1
[K]
formula ° (IX), which are described in WO 2005/019373 A2, wherein the symbols have the following meanings:
M is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the respective metal atom;
Carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;
L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a π complex with M1; n1 is the number of carbene ligands, where n1 is at least 1 and when n1 > 1 the carbene ligands in the complex of the formula I can be identical or different;
ml is the number of ligands L, where ml can be 0 or≥ 1 and when ml > 1 the ligands L can be identical or different;
o is the number of ligands K, where o can be 0 or≥ 1 and when o > 1 the ligands K can be identical or different;
where the sum n1 + ml + o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n1 is at least 1.
More preferred are metal-carbene complexes of the general formula
Figure imgf000087_0001
(IXa), which are described in WO2011/073149, where M , n1 , Y, A2', A3', A A^, R51 , R52, RSS, R54, RSS, Rse, RS?, RSS, R59, κ, L, ml and o1 are each defined as follows:
M is Ir, or Pt,
n1 is an integer selected from 1 , 2 and 3,
Y is N R51 , O, S or C(R25)2,
A2', A3', A4', and A5'are each independently N or C, where 2 A' = nitrogen atoms and at least one carbon atom is present between two nitrogen atoms in the ring,
R51 is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical op- tionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
R52, R53, R54 anc| R5s are each, jf A2', A3', A4' and/or A5' is N, a free electron pair, or, if A2', A3', A4' and/or A5' is C, each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one het- eroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
R53 and R54 together with A3' and A4' form an optionally substituted, unsaturated ring optionally interrupted by at least one further heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms,
R56, R57, R58 and R59 are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, cycloheteroalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
R56 and R57, R57 and R58 or R58 and R59, together with the carbon atoms to which they are bonded, form a saturated, unsaturated or aromatic, optionally substituted ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms, and/or
if A5' is C, R55 and R56 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, an aromatic unit, heteroaromatic unit and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which is optionally fused a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms,
R25 is independently a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon at- oms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
K is an uncharged mono- or bidentate ligand,
L is a mono- or dianionic ligand, preferably monoanionic ligand, which may be mono- or bidentate,
ml is 0, 1 or 2, where, when ml is 2, the K ligands may be the same or different, o1 is 0, 1 or 2, where, when o1 is 2, the L ligands may be the same or different.
Figure imgf000088_0001
(BE-3), 5
Figure imgf000089_0001
Figure imgf000090_0001
90
Figure imgf000091_0001
Figure imgf000092_0002
Figure imgf000092_0001
(BE-51), (BE-52),
Figure imgf000093_0001
Figure imgf000094_0001
(BE-75), (BE-76), 94
Figure imgf000095_0001
Figure imgf000096_0001
96
Figure imgf000097_0001
97
Figure imgf000098_0001
Figure imgf000099_0001
The compound of formula IX is more preferably a compound (BE-1 ), (BE-2), (BE-7), (BE- 12), (BE-16), (BE-64), or (BE-70). The most preferred phosphorescent blue emitters are compounds (BE-1 ) and (BE-12).
The homoleptic metal-carbene complexes may be present in the form of facial or meridional isomers, preference being given to the facial isomers.
Suitable carbene complexes of formula (IX) and their preparation process are, for example, described in WO201 1/073149.
The compounds of the present invention can also be used as host for phosphorescent green emitters. Suitable phosphorescent green emitters are, for example, specified in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151 , US20110227049, WO201 1090535, WO2012/08881 , WO20100056669, WO20100118029, WO20100244004, WO201 1109042, WO2012166608, US20120292600, EP2551933A1 ; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO 2012053627; US6921915, US20090039776; and JP2007123392.
Examples of suitable phosphorescent green emitters are shown below: 99
Figure imgf000100_0001
100
Figure imgf000101_0001
Figure imgf000102_0001
(GE-36), (GE-37),
Figure imgf000103_0001
Host (matrix) materials
The light-emitting layer may comprise further components in addition to the emitter materi- al. For example, a fluroescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material. In addition - in a preferred embodiment - a matrix material can be used. This matrix material may be a polymer, for example poly(N- vinylcarbazole) or polysilane. The matrix material may, however, be a small molecule, for example 4,4'-N,N'-dicarbazolebiphenyl (CDP=CBP) or tertiary aromatic amines, for exam- ple TCTA.
In a preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of the formula la, lb, lc, Id, or le, very especially la', lb', lc', Id', or le', is used as matrix material. Examples of preferred compounds of formula I are com- pounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G- 1 to E-20 shown above.
In a preferred embodiment, the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of at least one of the aforementioned emitter materials and 60 to 98% by weight, preferably 75 to 95% by weight, of at least one of the aforementioned ma- trix materials - in one embodiment at least one compound of the formula I - where the sum total of the emitter material and of the matrix material adds up to 100% by weight.
Suitable metal complexes for use together with the compounds of the formula I as matrix material in OLEDs are, for example, also carbene complexes as described in
WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/1 13704, WO 2007/115970, WO 2007/115981 and WO 2008/000727.
Further suitable host materials, which may be small molecules or (co)polymers of the small molecules mentioned, are specified in the following publications: WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37, WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (compounds 1 to 46 and Host-1 to Host-39 and Host-43), WO2009008100 compounds No.1 to No.67, preferably No.3, No.4, No.7 to No. 12, No.55, No.59, No. 63 to No.67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No.64, No.65, and No. 67, WO2009008099 compounds No. 1 to No. 110, WO20081401 14 compounds 1-1 to 1-50, WO2008090912 compounds OC-7 to OC-36 and the polymers of Mo-42 to Mo-51 , JP2008084913 H-1 to H-70, WO2007077810 compounds 1 to 44, preferably 1 , 2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers of monomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the (poly- mers of) compounds 1-1 to 1-36, WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298 the (co)polymers based on the monomers 1 to 75, JP2009170764, JP2009135183 the (co)polymers based on the monomers 1-14, WO2009063757 preferably the (co)polymers based on the monomers 1-1 to 1-26, WO2008146838 the compounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 the
(co)polymers based on the monomers 1-1 to 1-26, JP2008066569 the (co)polymers based on the monomers 1-1 to 1-16, WO2008029652 the (co)polymers based on the monomers 1-1 to 1-52, WO2007114244 the (co)polymers based on the monomers 1-1 to 1-18, JP2010040830 the compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and the (co)polymers based on the monomers HD-1 to HD-12, JP2009021336, WO2010090077 the compounds 1 to 55, WO2010079678 the compounds H1 to H42, WO2010067746, WO2010044342 the compounds HS-1 to HS-101 and Poly-1 to Poly-4, JP2010114180 the compounds PH-1 to PH-36, US2009284138 the compounds 1 to 11 1 and H1 to H71 , WO2008072596 the compounds 1 to 45, JP2010021336 the compounds H-1 to H-38, pref- erably H-1 , WO2010004877 the compounds H-1 to H-60, JP2009267255 the compounds 1-1 to 1-105, WO2009104488 the compounds 1-1 to 1-38, WO2009086028,
US2009153034, US2009134784, WO2009084413 the compounds 2-1 to 2-56,
JP20091 14369 the compounds 2-1 to 2-40, JP2009114370 the compounds 1 to 67, WO2009060742 the compounds 2-1 to 2-56, WO2009060757 the compounds 1-1 to 1-76, WO2009060780 the compounds 1-1 to 1-70, WO2009060779 the compounds 1-1 to 1-42, WO2008156105 the compounds 1 to 54, JP2009059767 the compounds 1 to 20,
JP2008074939 the compounds 1 to 256, JP2008021687 the compounds 1 to 50,
WO2007119816 the compounds 1 to 37, WO2010087222 the compounds H-1 to H-31 , WO2010095564 the compounds HOST-1 to HOST-61 , WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446, WO06128800, WO2012014621 ,
WO2012105310, WO2012/130709 and European patent applications EP12175635.7 and EP12185230.5. and EP12191408.9 (in particular page 25 to 29 of EP12191408.9).
The above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules. 72 (for example,
Figure imgf000104_0001
; best results are
Figure imgf000104_0002
achieved if said compounds are combined with );
Figure imgf000105_0001
In a particularly preferred embodiment, one or more compounds of the general formula (X) specified herein
Figure imgf000105_0002
X is NR, S, O or PR;
R is aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi;
A200 js .N R206R207, _p(O)R208R209 _pR210 211 _ -S(0)2R212, -S(0)R213, -SR214 0ΐ -OR215;
R221 R222 anc| R223 are independently of each other aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi, wherein at least on of the groups R221, R222, or R223 is aryl, or heteroaryl; R224 and R225 are independently of each other alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl, a group A200, or a group having donor, or acceptor characteristics;
n2 and m2 are independently of each other 0, 1 , 2, or 3;
R206 and R207form together with the nitrogen atom a cyclic residue having 3 to 10 ring atoms, which can be unsubstituted, or which can be substituted with one, or more substitu- ents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and/or which can be annulated with one, or more further cyclic residues having 3 to 10 ring atoms, wherein the annulated residues can be unsubstituted, or can be substituted with one, or more substituents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and R208i R209i R2io_ 2i i _ 212_ 213_ R214 u nc| R215 are independently of each other aryl, het
Figure imgf000106_0001
(in particular pages on 19 to 26 and in tables on pages 27 to 34, pages 35 to 37 and pages 42 to 43).
Additional host materials on basis of dibenzofurane are, for example, described in
US2009066226, EP1885818B1 , EP1970976, EP1998388 and EP2034538. Examples of particularly preferred host materials are shown below:
Figure imgf000106_0002
Figure imgf000107_0001
107
Figure imgf000108_0001
Figure imgf000109_0001
In the above-mentioned compounds T is O, or S, preferably O. If T occurs more than one time in a molecule, all groups T have the same meaning. Compounds
Figure imgf000109_0002
Figure imgf000110_0001
(SH-10) are most preferred. Hole/exciton blocking layer (f):
Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. The hole blocking layer may be disposed between the emitting layer (e) and electron transport layer (g), to block holes from leaving layer (e) in the direction of electron transport layer (g). Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
Additional hole blocker materials typically used in OLEDs are 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline (bathocuproin, (BCP)), bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll) (BAIq), phenothiazine S,S-dioxide derivates and 1 ,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-transport material. Further suitable hole blockers and/or electron conductor materials are 2,2',2"-(1 ,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4- biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole, 8-hydroxyquinolinolatolithium, 4- (naphthalen-1-yl)-3,5-diphenyl-4H-1 ,2,4-triazole, 1 ,3-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4- oxadiazo-5-yl] benzene, 4,7-diphenyl-1 ,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-1 ,2,4-triazole, 6,6'-bis[5-(biphenyl-4-yl)-1 ,3,4-oxadiazo-2-yl]-2,2'-bipyridyl, 2- phenyl-9, 10-di(naphthalene-2-yl)anthracene, 2,7-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4-oxadiazo- 5-yl]-9,9-dimethylfluorene, 1 ,3-bis[2-(4-tert-butylphenyl)-1 ,3,4-oxadiazo-5-yl]benzene, 2- (naphthalene-2-yl)-4,7-diphenyl-1 ,10-phenanthroline, tris(2,4,6-trimethyl-3-(pyridin-3- yl)phenyl)borane, 2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1 , 10-phenanthroline, 1-methyl-2- (4-(naphthalene-2-yl)phenyl)-1 H-imidazo[4,5-f][1 ,10]phenanthroline. In a further embodi- ment, it is possible to use compounds which comprise aromatic or heteroaromatic rings joined via groups comprising carbonyl groups, as disclosed in WO2006/100298, disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, dis- ilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and dis- ilylbenzothiophene S,S-dioxides, as specified, for example, in PCT applications
WO2009/003919 and WO2009003898 and disilyl compounds as disclosed in
WO2008/034758, as a blocking layer for holes/excitons (f).
In another preferred embodiment compounds (SH-1 ), (SH-2), (SH-3), SH-4, SH-5, SH-6, (SH-7), (SH-8), (SH-9) and (SH-10) may be used as hole/exciton blocking materials.
Electron transport layer (g):
Electron transport layer may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Suitable electron-transporting materials for layer (g) of the inventive OLEDs comprise metals chelated with oxinoid compounds, such as tris(8- hydroxyquinolato)aluminum (Alq3), compounds based on phenanthroline such as 2,9- dimethyl-4,7-diphenyl-1 ,10-phenanthroline (DDPA = BCP), 4,7-diphenyl-1 , 10- phenanthroline (Bphen), 2,4,7,9-tetraphenyl-1 , 10-phenanthroline, 4,7-diphenyl-1 , 10- phenanthroline (DPA) or phenanthroline derivatives disclosed in EP1786050, in
EP1970371 , or in EP1097981 , and azole compounds such as 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole (TAZ). It is likewise possible to use mixtures of at least two materials in the electron-transporting layer, in which case at least one material is electron-conducting. Preferably, in such mixed electron-transport layers, at least one phenanthroline compound is used, preferably BCP, or at least one pyridine compound according to the formula (VIII) below, preferably a compound of the formula (Vlllaa) below. More preferably, in mixed electron-transport layers, in addition to at least one phenanthroline compound, alkaline earth metal or alkali metal hy- droxyquinolate complexes, for example Liq, are used. Suitable alkaline earth metal or alkali metal hydroxyquinolate complexes are specified below (formula VII). Reference is made to WO2011/157779. The electron-transport layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1 , 1 July 2003 (p- doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23 June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89 - 103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, it is possible to use mixtures which lead to electrical n-doping of the electron- transport layer. n-Doping is achieved by the addition of reducing materials. These mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, CS2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li3N, Rb2C03, dipotassium phthalate, W(hpp)4 from EP1786050, or with compounds described in EP1837926B1 , EP1837927, EP2246862 and WO2010132236.
In a preferred embodiment, the electron-transport layer comprises at least one compound of the general formula (VII)
Figure imgf000112_0001
, in which
R32 and R33 are each independently F, d-Cs-alkyl, or C6-Ci4-aryl, which is optionally substituted by one or more d-Cs-alkyl groups, or
two R32 and/or R33 substituents together form a fused benzene ring which is optionally substituted by one or more d-Cs-alkyl groups;
a and b are each independently 0, or 1 , 2 or 3,
M1 is an alkaline metal atom or alkaline earth metal atom,
p is 1 when M1 is an alkali metal atom, p is 2 when M1 is an earth alkali metal atom.
A very particularly preferred compound of the formula (VII) is
Figure imgf000112_0002
(Liq), which may be present as a single species, or in other forms such as LigQg in which g is an integer, for example LkQe- Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.
In a further preferred embodiment, the electron-transport layer comprises at least one compound of the formul
Figure imgf000112_0003
(VIII), in which
R34, R35, R36, R37, R34', R35', R36' and R37'are each independently H , Ci-Cis-alkyl, C1-C18- alkyl which is substituted by E and/or interrupted by D, C6-C24-aryl, C6-C24-aryl which is substituted by G, C2-C2o-heteroaryl or C2-C2o-heteroaryl which is substituted by G, Q is an arylene or heteroarylene group, each of which is optionally substituted by G;
D is -CO-; -COO-; -S-; -SO-; -SO2-; -0-; -NR4°-; -SiR45R46-; -POR47-; -CR38=CR39-; or -C≡
E is -OR44; -SR44; -NR40R4i ; -COR43; -COOR42; -CONR40R4i ; -CN; or F; G is E, Ci-Ci8-alkyl, Ci-Cis-alkyl which is interrupted by D , Ci-Ci8-perfluoroalkyl, C1-C18- alkoxy, or Ci-Cis-alkoxy which is substituted by E and/or interrupted by D,
in which
R38 and R39 are each independently H , C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; R40 and R41 are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; or
R40 and R41 together form a 6-membered ring;
R42 and R43 are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
R44 is C6-Ci8-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; C1-C18- alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
R45 and R46 are each independently Ci-Cie-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl,
R47 is Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl.
Preferred compounds of the formula (VIII) are compounds of the formula (Villa)
in which Q is:
Figure imgf000113_0001
R48 is H or Ci-Cis-alkyl and
Figure imgf000113_0002
R48' is H , Ci-Cis-alkyl or or
Particular preference is given to a compound of the formula
Figure imgf000113_0003
In a further, very particularly preferred embodiment, the electron-transport layer comprises a compound Liq and a compound ETM-2. In a preferred embodiment, the electron-transport layer comprises the compound of the formula (VII) in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of the compounds of the formulae (VII) and the amount of the compounds of the formulae (VIII) adds up to a total of 100% by weight.
The preparation of the compounds of the formula (VIII) is described in J. Kido et al., Chem. Commun. (2008) 5821-5823, J. Kido et al., Chem. Mater. 20 (2008) 5951-5953 and JP2008/127326, or the compounds can be prepared analogously to the processes disclosed in the aforementioned documents.
It is likewise possible to use mixtures of alkali metal hydroxyquinolate complexes, preferably Liq, and dibenzofuran compounds in the electron-transport layer. Reference is made to WO2011/157790. Dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790 are preferred, wherein dibenzofuran compound
Figure imgf000114_0001
(A-10; = ETM-1) is most preferred.
In a preferred embodiment, the electron-transport layer comprises Liq in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of Liq and the amount of the dibenzofuran compound(s), especially ETM-1 , adds up to a total of 100% by weight.
In a preferred embodiment, the electron-transport layer comprises at least one phenanthro- line derivative and/or pyridine derivative.
In a further preferred embodiment, the electron-transport layer comprises at least one phe- nanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex. In a further preferred embodiment, the electron-transport layer comprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790, especially ETM-1.
In a further preferred embodiment, the electron-transport layer comprises a compound described in WO2012/11 1462, WO2012/147397, WO2012014621 , such as, for example, a
Figure imgf000115_0001
compound of formula (ETM-3), US2012/0261654,
Figure imgf000115_0002
Electron injection layer (h):
The electron injection layer may be any layer that improves the injection of electrons into an adjacent organic layer. Lithium-comprising organometallic compounds such as 8- hydroxyquinolatolithium (Liq), CsF, NaF, KF, CS2CO3 or LiF may be applied between the electron transport layer (g) and the cathode (i) as an electron injection layer (h) in order to reduce the operating voltage.
Cathode (i):
The cathode (i) is an electrode which serves to introduce electrons or negative charge carriers. The cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1 , for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
In general, the different layers, if present, have the following thicknesses:
anode (a): 500 to 5000 A (angstrom), preferably 1000 to 2000 A;
hole injection layer (b): 50 to 1000 A, preferably 200 to 800 A,
hole-transport layer (c): 50 to 1000 A, preferably 100 to 800 A, exciton blocking layer (d): 10 to 500 A, preferably 50 to 100 A,
light-emitting layer (e): 10 to 1000 A, preferably 50 to 600 A,
hole/ exciton blocking layer (f): 10 to 500 A, preferably 50 to 100 A,
electron-transport layer (g): 50 to 1000 A, preferably 200 to 800 A,
electron injection layer (h): 10 to 500 A, preferably 20 to 100 A,
cathode (i): 200 to 10 000 A, preferably 300 to 5000 A.
The person skilled in the art is aware (for example on the basis of electrochemical studies) of how suitable materials have to be selected. Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
In addition, it is possible that some of the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport. The selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.
The inventive OLED can be produced by methods known to those skilled in the art. In general, the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass, inorganic semi- conductors or polymer films. For vapor deposition, it is possible to use customary techniques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others. In an alternative process, the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art.
Use of the compounds of the formula I in at least one layer of the OLED, preferably in the light-emitting layer (preferably as a matrix material), charge transport layer and/or in the charge/exciton blocking layer makes it possible to obtain OLEDs with high efficiency and with low use and operating voltage. Frequently, the OLEDs obtained by the use of the compounds of the formula I additionally have high lifetimes. The efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs. For example, high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermediate layer of LiF, can be used. Moreover, additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence.
The OLEDs may further comprise at least one second light-emitting layer. The overall emission of the OLEDs may be composed of the emission of the at least two light-emitting layers and may also comprise white light. The OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual dis- play units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Further devices in which the inventive OLEDs can be used are, for example, keyboards; items of clothing; furniture; wallpaper. In addition, the present invention relates to a device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.
Examples
Figure imgf000117_0001
a) A mixture of 4.80 g (23.0 mmol) 6H-benzimidazolo[1 ,2-a]benzimidazole, 5.10 g (23.0 mmol) 2-bromo-4-fluoro-2-nitrobenzene and 3.68 g (27.0 mmol) potassium carbonate in 63 ml dimethylsulfoxide (DMSO) is stirred under argon at 100 °C for 1 h, cooled to 20 °C and poured into 240 ml water. The product is filtered off and is washed with water. Yield 8.84 g (100 %).
1 H NMR (400 MHz, CDCIs): δ 8.42 (s, 1 H), 8.20 (s, 2H), 7.82-7.89 (m, 3H), 7.70-7.72 (m, 1
Figure imgf000117_0002
b) 2.00 g (4.91 mmol) of the product of example 1 a, 0.81 g (5.40 mmol) 1 ,3- dihydrobenzimidazole-2-thione, 4.00 g (12.28 mmol) caesium carbonate in 16 ml DMSO are stirred at 130 °C for 1 h and then at 170 0 for 4 h. The reaction mixture is diluted with water and the product is filtered off and decocted in 20 ml ethanol.
1 H NMR (400 MHz, CDC ): δ 8.29 (d, J= 2.0 Hz, 1 H), 8.15 (d, J= 8.58 Hz, 1 H), 7.99-8.06 (m, 2H), 7.88-7.91 8 (m, 3H), 7.81 (d, J= 7.6 Hz, 1 H), 7.60-7.62 (m, 1 H), 7.34-7.51 (m, 6H). MS (APCI(pos), m/z): 429 (M+i).
Example 2
Figure imgf000118_0001
a) Example 1a) is repeated, except that instead of 6H-benzimidazolo[1 ,2-a]benzimidazole 9H-carabazole is used.
Figure imgf000118_0002
b) Example 1a) is repeated, except that instead of the product of Example 1 a) the product of Example 2a) is used.
Figure imgf000118_0003
a) 76.9 g (0.460 mol) carbazole and 104 g (0.460 mol) 1-iodopyrrolidine-2,5-dione (NIS) in 100m ml acetic acid are stirred under nitrogen at 20 °C. After 5 h the product is filtered off and crystalized from 900 ml ethanol using 2 g charcoal. The ethanol solution is filtered hot and cooled to 20 °C. The product is filtered off (yield: 59.5 g (44 %)).
Figure imgf000118_0004
b) 19.7 g (67.0 mmol) 3-iodo-9H-carbazole and 2.95 g (73.7 mmol) sodium hydrid 60 % dispersion in mineral oil in 500 ml tetrahydrofuran (THF) is stirred at 50 °C under nitrogen for 1 h. 12.8 g (67.0 mmol) 4-methylbenzenesulfonyl chloride in 100 ml THF are added at 20 °C. The reaction mixture is stirred for 1 h at 20 °C and is than stirred for 1 h at 50 °C. The solution is filtered and the solvent is distilled of. 200 ml ethyl acetate are added and the organic phase is washed with a solution of citric acid, sodium hydrogen carbonate and water. The solvent is partly removed until the product starts to crystalize and is filtered off. The product is washed with methanol (yield: 23 g (79 %)).
Figure imgf000119_0001
c) 36.0 g (174 mmol) 6H-benzimidazolo[1 ,2-a]benzimidazole, 77.8 (174 mmol) 3-iodo-9-(p- tolylsulfonyl) carbazole, 106 g (0.500 mol) potassium phosphate, 5.5 g (28.9 mmol) copper iodide, and 11 1 g (0.972 mol) trans-cyclohexane-1.2-diamimne in 900 ml dioxane are stir- red at 100 °C for 48 h under nitrogen. The product is filtered off, washed with dioxane and e
Figure imgf000119_0002
d) A solution of 1 1.3 g (202 mmol) potassium hydroxide in 500 ml ethanol is added to 53 g (101 mmol) 5-[9-(p-tolylsulfonyl)carbazol-3-yl]benzimidazolo[1 ,2-a]benzimidazole in boiling 500 ml ethanol within 5 minutes under nitrogen. After 5 h the product is filtered off and
Figure imgf000119_0003
e) 931 mg (2.50 mmol) 5-(9H-carbazol-3-yl)benzimidazolo[1 ,2-a]benzimidazole, 578 mg (2.60 mmol) 2-bromo-4-fluoro-1-nitro-benzene and 435 mg (3.20 mmol) potassium carbonate in 10 ml DMSO are stirred under nitrogen at 100 °C. After 16 h the reaction mixture is poured into water and the product is filtered off. The product is washed with water and ethanol (yield: 1.21 g (85 %)). 1 H NMR (400 MHz, CDCIs): δ 8.45-8.46 (m, 1 H), 8.21-8.24 (m, 2H), 8.1 1 (d, J
7.88-7.96 (m. 4H), 7.71-7.74 (m, 1 H), 7.53-7.60 (m, 3H), 7.38-7.50 (m, 6H).
+1).
Figure imgf000120_0001
f) 1.14 g (2.00 mmol) 5-[9-(3-bromo-4-nitro-phenyl) carbazole-3-yl]benzimidazolo [1 ,2- a]benzimidazole and 330 mg (2.20 mmol) 1 ,3-dihydrobenzimidazole-2-thione and 1.63 g (5.00 mol) caesium carbonate in 10 ml DMSO are stirred under nitrogen at 100 °C for 1 h. The reaction mixture is stirred at 180 °C for 3 h, is poured into water. Sodium chloride is added and the water phase is extracted with THF. The organic phase is dried with magne- sium sulphate. Column chromatography on silica gel with toluene/ethylacetat 10/1 and then 5/1 give the product (yield: 800 mg (67 %)).
1 H NMR (400 MHz, THF-d8): δ 8.68 (d, J= 2Hz, 1 H), 8.48 (d, J=8.5 Hz, 1 H), 8.26-8.32 (m, 3H), 7.98-8.04 (m, 2H), 7.90-7-94 (m, 2H), 7.78-7.81 (m, 1 H),
7.60-7.68 (m, 3H), 7.21-7.51 (m, 9H). MS (APCI(pos), m/z): 595 (M+i).
Figure imgf000120_0002
a) 1.69 g (7.50 mmol) N-lodsuccinimid are added to 1.12 g (5.00 mmol) of benzimidazo- lo[2,1-b][1 ,3]benzothiazole (prepared in anlogy to Organic & Biomolecular Chemisty 10 (2012) 7944) in 20 ml acetic acid and 1 ml trifluoracetic acid at 120 °C under nitrogen. After 1 h 1.69 g (7.50 mmol) N-lodsuccinimid are added. After 1 h the reaction mixture is poured into 10 % sodium dithionite solution and the water phase is extracted with dichloromethane. The organic phase is dried with magnesium sulphate and the solvent is removed in vac- cum. The product is crystallized from dibutylether (yield = 1.30 g (75 %)).
H NMR (400 MHz, CDCI3): δ 8.34 (d, J= 1.4 Hz, 1 H), 7.97 (d, J=8.0 Hz, 1 H), 7.75-7.82 (m,
Figure imgf000120_0003
b) 4.02 g (35.2 mol) trans-cyclohexane-1.2-diamine are added to 800 mg (1.96 mmol) 9- iodobenzimidazolo[2,1-b][1 ,3]benzothiazole 490 mg (2.35 mmol) 6H-benzimidazolo[1 ,2- a]benzimidazole, 1 ,37 g (6.45 mmol) potassium phosphate, 370 mg (0.20 mmol) copper iodide in 10 ml dioxane. The reaction mixture is stirred for 27 h at 100 °C under nitrogen and cooled to 25 °C. The product is filtered off and washed with water and methanol. 100 ml chloroform is added and the product is stirred for 30 minutes. The solid is filtered off and product precipitating from the chloroform phase is filtered off (yield: 1 10 mg (13 %)). 1 H NMR (400 MHz, CF3COOD): δ 9.24 (s, 1 H), 8.66-8.69 8 (m, 2H), 8.43-8.8.56 (m, 4H), 8.02-8.20 (m, 7H), 7.93-7.95 (m, 1 H).
MS (APCI(pos), m/z): 430 (M+i).
Example 5
Figure imgf000121_0001
a) 11.8 g (78.3 mmol) 2-mercaptobenzimidazole and 58.0 g (178 mmol) caesium carbonate are added to 20.0 g (71.2 mmol) 1 ,4-dibromo-2-nitro-benzene in 400 ml DMSO (dimethyl sulfoxide). The reaction mixture is stirred under nitrogen for 1 h at 130 °C and then for 2 h at 180 °C. The reaction mixture is cooled to 20°C and the precipitated product is filtered off. The product is soxhlet extracted with 300 ml ethanol and the product is filtered off (yield: 13.5 g (63 %)). H NMR (400 MHz, CDC ): δ 8.13 (d, J=1.7 Hz, J= 1 H), 7.96.7.99 (m, 1 H), 7.87-7.91 (m, 1 H), 7.66 (d, J= 8.5 Hz, 1 H), 7.43-7.58 (m, 3H).
Figure imgf000121_0002
b) 9.17 g (40.7 mmol) N-iodosuccinimide (NIS) is added to 13.0 g (42.9 mmol) 2- bromobenzimidazolo[2,1-b][1 ,3]benzothiazole in 175 ml acetic acid and 9 ml trifluoroacetic acid at 100 °C under nitrogen. The product is stirred for 2.5 g at 100 °C and the precipitated product is filtered off. The product is washed with a 10 % sodium dithionite solution, water and methanol. The product is soxhlet extracted with 300 ml methyl ethyl ketone and the product is filtered off (yield: 15.1 g (82 %)). Ή NMR (400 MHz, [D6]DMSO): δ 8.95 (d, J=1.5 Hz, J= 1 H), 8.76 (d, J=1.8 Hz, J= 1 H), 8.05 (d, J=8.5 Hz, 1 H) 7.73 (dd, J=1.5 Hz, J=8.5 Hz, 1 H), 7.66 (dd, J= 1.9 Hz, J= 8.5 Hz), 7.57 (d, J= 8.5 Hz)
Figure imgf000121_0003
c) 9.74 g (58.3 mmol) carbazole, 14.8 g (69.9 mmol) potassium phosphate tribasic, 890 mg (4.7 mmol) copper iodide and 26.6 g (233 mmol) cis/trans 1 ,2-diaminocyclohexane (DACH) are added to 10.0 g (23.3 mmol) 2-bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole in 100 ml 1 ,4-dioxane. The reaction mixture is stirred at 100 °C under nitrogen for 75 h and then filtered on Hyflo Super Cel (CAS number 91053-39-3) with dichloromethane. The di- chloromethane is distilled off and the solution is poured into methanol. The product is filtered off, filtered on silica gel with dichloromethane and then dichloromethane/ethanol 95/5. The solvent is concentrated to a volume of 10 ml ethanol. 100 ml methanol are added and the product is filtered off (yield: 6.38 g (49 %)). H NMR (400 MHz, [D8]THF): δ 8.63 (d, J=1.9 Hz, J= 1 H), 8.60 (d, J=1.7 Hz, J= 1 H), 8.24 (d, J=8.3 Hz, 1 H) 8.09-8.12 (m, 4H), 8.04 (d, J= 8.5 Hz, 1 H), 7.67 (dd, J=1.9 Hz, J=8.4 Hz, 1 H), 7.60 (dd, J= 2.0 Hz, J= 8.5 Hz), 7.30-
Figure imgf000122_0001
00 g (4.66 mmol) 2-bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole, 2.04 g (6.99 mmol) (2,4,6-triisopropylphenyl)boronic acid, 3.96 g (18.6 mmol) potassium phosphate tribasic in 80 ml toluene, 15 ml dioxane and 15 ml water are degased with argon. 340 mg (0.84 mmol) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (sPhos) and 213 mg (0.23 mmol) tris(dibenzylidenaceton)dipalladium(0) (Pd2(dba)3) are added. The reaction mixture is degased with argon and stirred at 110 °C for 27 h under argon. 40 ml 1 % sodiumcyanide solution is added to the reaction mixture and the reaction mixture is refluxed for 1 h. Water is added and the water phase is extracted with dichloromethane. The organic phase is dried with magnesium sulfate and the solvent is destilled off. The product is filtered on silica gel with dochloromethan. The product is decocted with methanol (yield: 1.89 g (65 %)). 1H NMR (400 MHz, [D6]DMSO): δ 8.47-8.49 (m, 2 H), 8.09 (d, J = 8.1 Hz, 1 H), 7.77 (d, J= 8.2 Hz, 1 H), 7.18 (dd, J = 1.4 Hz, J= 8.1 Hz, 1 H), 7.12 (dd, J= 1.4 Hz, J= 8.26 Hz, 2H), 7.06 (s, 2H), 7.04 (s, 1 H), 2.85-2.91 (m, 2H), 2.47-2.55 (m, superimposed), 1.21 (d, J= 6.9 Hz, 12H), 1.00-1.04 (m, 24H). MS (APCI(pos), m/z): 629 (M+i).
Figure imgf000122_0002
2,9-di(dibenzofuran-4-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 2-bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole and dibenzofuran-4-ylboronic acid.
MS (APCI(pos), m/z): 657 (M+i). Example 8
Figure imgf000123_0001
he synthesis of 9-[3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl]carbazole is described in Chem. Mater. 20 (2008) 1691-1693. 2-(3-carbazol-9-ylphenyl)benzimidazolo[2,1- b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 2-bromo-9-iodo- benzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)phenyl]carbazole. Palladium acetate is used instead of
tris(dibenzylidenaceton)dipalladium(0) (Pd2(dba)3) (yield: 330 mg (21 %)). 1 H NMR (400 MHz, [D6]DMSO): δ 8.52-8.56 (m, 2H), 8.30 (s, 1 H), 8.28 (s, 1 H), 8.18-8.21 (m, 2H), 8.08 (d, J= 7.8 Hz, 1 H), 7.83-7.90 (m, 2H), 7.70-7.77 (m, 2H), 7.305-7.54 (m, 8H)
Figure imgf000123_0002
4.02 g (13.3 mmol) 2-bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole, 1.00 g (6.03 mmol) (2,4,6-triisopropylphenyl)boronic acid, 5.12 g (24.1 mmol) potassium phosphate tri- basic in 60 ml toluene, 15 ml dioxane and 15 ml water are degased with argon. 450 mg (1.1 mmol) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (sPhos) and 280 mg (0.30 mmol) tris(dibenzylidenaceton)dipalladium(0) (Pd2(dba)3) are added. The reaction mixture is degased with argon and stirred at 90 °C for 33 h under argon. 30 ml 1 % sodiumcyanide solution is added to the reaction mixture and the reaction mixture is refluxed for 1 h. Water is added and the water phase is extracted with dichloromethane. The precipitated product is filtered off. Soxlet extraction with methyl-ethyl ketone results in the product (yield: 590 mg (19 %)). H NMR (400 MHz, [D6]DMSO): δ 8.71-8.73 (m, 4H), 8.32 (s, 1 H), 8.23 (s, 1 H), 8.12 (s, 1 H), 7.91-7.97 (m, 4H), 7.78-7.80 (m, 2H), 7.72 (t, J = 7.7 Hz, 1 H), 7.42-7.48 (m, 4H). MS (APCI(pos), m/z): 523 (M+i).
Example 10
Figure imgf000123_0003
2-(2,4,6-triisopropylphenyl)benzimidazolo[2,1-b][1 ,3]benzothiazole is perpared in aniogy to Example 6 starting from 2-bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole and (2,4,6- triisopropylphenyl)boronic acid (yield: 1.58 g (54 %)). Ή NMR (400 MHz, CDCb): δ 7.87- 7.91 (m, 2H), 7.79-7.82 (m, 2H), 7.43-7.47 (m, 1 H), 7.34-7.39 (m, 1 H), 7.25-7.28 (m, 1 H), 7.15 (s, 2H), 3.01 (sep, J= 7 Hz, 1 H), 2.66 (sep, J= 6.9 Hz, 2H), 1.37 (d, J=6.9, 6H), 1.19 (d, J= 7 Hz, 6H), 1.14 (d, J= 7 Hz, 6 H).
Figure imgf000124_0001
2,9-di(dibenzofuran-4-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[8-(4,4,5,5- tetramethyl-1 ,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole. 9-[8-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole is prepared as described in
WO12130709. H NMR (400 MHz, [D6]DMSO): δ 8.80 (d, J= 1.8 Hz, 1 H), 8.66 (s, 1 H), 8.58 (d, J= 2.1 Hz), 1 H), 8.56 (d, J=8.4 Hz, 1 H), 8.30 (d, J= 7.8 Hz, 2H) 8.14 (dd, J= 2.0 Hz, J= 8.7 Hz, 1 H), 8.09 (dd, J= 0.9 Hz, J= 8.1 Hz, 1 H), 8.04 (d, J= 8.7 Hz, 1 H), 7.93 (d, J= 8.6 Hz, 1 H), 7.86 (s, 2H), 7.78 (dd, J= 2.2 Hz, J= 8.6 Hz), 7.61-7.66 (m, 1 H), 7.42-7.50 (m, 5 H), 7.31-7.35 (m, 2H). MS (APCI(pos), m/z): 556 (M+i).
Figure imgf000124_0002
9-[8-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole is prepared as described in WO12130709. 9-(8-carbazol-9-yldibenzofuran-2-yl)benzimidazolo[2,1- b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 2-bromo- benzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[8-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)dibenzofuran-2-yl]carbazole (yield: 1.01 g (55%)). H NMR (400 MHz, CDCb): δ 8.21- 8.26 (m, 5H), 8.07 (d, J= 7.3, 1 H), 7.81-7.91 (m, 5H), 7.69-7.73 (m, 2H), 7.40-7.49 (m, 6H), 7.32-7.37 (m, 2H). MS (APCI(pos), m/z): 556 (M+i). Example 13
Figure imgf000125_0001
The synthesis of 9-phenyl-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)carbazole is described in WO2012/023947A1. 2-(9-phenylcarbazol-3-yl)benzimidazolo[2,1- b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 2-bromo-9-iodo- benzimidazolo[2,1-b][1 ,3]benzothiazole and 9-phenyl-3-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)carbazole. H NMR (400 MHz, CDC ): δ 8.46 (d, J=1.4 Hz, 1 H), 8.25- 8.29 (m, 2H), 8.09-8.12 (m 1 H), 7.89-7.92 (m, 1 H), 7.84 (d, J= 8.3 Hz, 1 H), 7.73-7.77 (m, 2H), 7.63-7.70 (m, 4H), 7.52-7.58 (m, 2H), 7.43-7.50 8m, 4H), 7.35-7.40 (m, 1 H).
Figure imgf000125_0002
1.00 g (2.86 mmol) 9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole, 1.12 g (4.28 mmol) tri- phenylsilane and 820 mg (5.71 mmol) potassium phosphate tribasic (water free) in 150 ml dimethylformamide are degassed with argon. 38 mg (0.090 mmol) rhodium(ll)-acetate is added and the reaction mixture is degassed with argon. The reaction mixture is stirred at 100 °C for 39 h under argon, poured into water and the water phase is extracted with di- chloromethane. The organic phase is washed with 1 % KCN solution in water. The organic phase is dried with magnesium sulfate. The solvent is distilled off. Column chromatography on silica gel with toluene/ ethyl acetate (gradient 100% to 1/1 ) results in 50 mg (4 %) of the product. MS (APCI(pos), m/z): 483 (M+i).
Exa
Figure imgf000125_0003
The synthesis of 4,4,5,5-tetramethyl-2-triphenylen-2-yl-1 ,3,2-dioxaborolane is described in Dyes and Pigments 101 (2014) 221-228. 2-Triphenylen-2-ylbenzimidazolo[2,1- b][1 ,3]benzothiazole (C-16) is prepared in analogy to Example 6 starting from 2-bromo- benzimidazolo[2,1-b][1 ,3]benzothiazole and 4,4,5,5-tetramethyl-2-triphenylen-2-yl-1 ,3,2- dioxaborolane. MS (APCI(pos), m/z): 551 (M+ ). Application Example 1
Determination of triplet energy
The triplet energies of the materials are directly determined from the onsets of the ured phosphorescence spectra of the thin films of neat materials.
Figure imgf000126_0001
second doctor-blading the solutions onto pre-cleaned quartz-slides with a thin film applicator of 30 μιτι slot width (Erichsen, Model 360 02082).
The 2% in PMMA films are prepared by dissolving 1 mg of the respective material in 370 μΙ of a dichloromethane solution containing 10 wt% PMMA. A thin film applicator of 60 μιη slot width (Erich used for doctor-blading.
Compound
Figure imgf000126_0002
(B-1 ) is deposited by vapor deposition to the quartz substrates at a rate of approx. 0.5-5 nm/min at about 10-6 mbar until approx. 60 nm thick film is formed.
For measurement the resulting thin film samples are inserted into a liquid-helium cryostat Optistat CF (Oxford Instruments) and cooled to a temperature of 4-5K. The phosphorescence spectra are measured with a fluorescence/phosphorescence spectrometer FLS- 920P (Edinburgh Instruments). The samples are excited with an electrically pulsed LED model UVTOP 315-HL-T039 (Fa. Roithner, Vienna) with a center wavelength of 320 nm and a pulse width of 5 μβ. The emission spectra are detected via time-gated spectroscopy with a delay-time of 260 \is. The triplet energies (Ti) are determined from the onset of the phosphorescence spectra, the results are shown in the table below.
Figure imgf000127_0002
Figure imgf000127_0001
Due to their triplet energies compounds B-1 , B-2 and F-12 are suitable as hosts for blue emitters. Due to their triplet energies compounds B-1 , B-2, F-12, C-14, D-14 and C-30 are suitable as hosts for green emitters.
Compound F-12 has a higher triplet energy than comparative compound CC-1 . That is, compound F-12 is, in principal, a better host for deep blue phosphorescent emitters.
Application Example 2
Detemination of IP (HOMO) and EA (LUMO) levels
Cyclic voltammetry and differential pulsed voltammetry are performed using a computer- controlled Metrohm Autolab PGSTAT12 potentiostat in a three-electrode single- compartment cell with a platinum or glassy carbon working electrode, a platinum wire counter electrode and an Ag/AgCI or Ag/Ag+ reference electrode. Anhydrous DMF (distilled over P2O5) is used as the solvent under an inert atmosphere, and 0.1 M tetra-n-butylammonium hexafluorophosphate (TBAPF6) is used as the supporting electrolyte. The samples are measured at a concentration of 1 mM. All potentials are internally referenced to the ferro- cene/ferrocenium (Fc/Fc+) couple.
The ionization potential (IP, HOMO level) and electron affinity (EA, LUMO level) are calculated using the following equations:
(1 ) IP [eV] = 1.4x(1.0xE0nset - Fc/Fc+E0nset) + 4.6 {Org. El. 2005, 6, 1 1-20) and
(2) EA [eV] = 1 .19*(1 .RedEi/2 - Fc/Fc+Ei/2) + 4.78 {Org. El. 2009, 10, 515-520)
Figure imgf000128_0001
Appl. Example Cpd. IP [eV] EA [eV]
2a CC-2 5.51 1.08
2b B-2 5.84 1.28
The electron affinity of the benzimidazolo[2,1-b][1 ,3]benzothiazole derivatives, such as, for example, compound B-2, of the present invention is higher than the electron affinity of corresponding 6H-benzimidazolo[1 ,2-a]benzimidazole derivatives, such as, for example, comparative compound CC-2. In general, the ionization potential of the benzimidazolo[2,1- b][1 ,3]benzothiazole derivatives of the present invention is also lower (higher absolute value) than the ionization potential of corresponding 6H-benzimidazolo[1 ,2-a]benzimidazole derivatives. That means, the benzimidazolo[2,1-b][1 ,3]benzothiazoles of the present application are in general superior electron injection, hole blocking and electron transporting units in comparison with benzimidazolo[1 ,2-a]benzimidazoles of the prior art.
Comparative Application Example 1
The ITO substrate used as the anode is first cleaned with an isopropanol in an ultrasonic bath. To eliminate any possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for further 30 minutes. This treatment also improves the hole injection properties of the ITO. Then Plexcore® OC AJ20-1000 (commercially available from Plextronics Inc.) is spin-coated and dried to form a hole injection layer (-40 nm). Thereafter, the organic materials specified below are applied by vapor deposition to the Plexcore® coated substrate at a rate of approx. 0.5-5 nm/min at about 10-7 -10-9 mbar. As a
Figure imgf000128_0002
hole transport material, compound (HTM-1 ; for preparation, see Ir com- plex (7) in the application WO2005/019373) is applied by vapor deposition in a thickness of 10 nm doped with MoOx (-10%) to improve the conductivity. As exciton and electron blocker, (HTM-1) is applied to the substrate with a thickness of 10 nm. Subsequently, a
Figure imgf000129_0001
mixture of 10% by weight of emitter compound, (BE-1 ), 5% by weight
Figure imgf000129_0002
of compound (HTM-1) and 85% by weight of compound
(CC-3) are applied by vapor deposition in a thickness of 40 nm. Subsequently, materi-
Figure imgf000129_0003
al (SH-2) is applied by vapour deposition with a thickness of 5 nm as a blocker. Ther electron transport layer is deposited
f 50% by weight of (ETM-1), and of 50% of
Figure imgf000129_0004
(Liq). Finally a 2 nm KF layer serves as an electron injection layer and a 100 nm-thick Al electrode completes the device.
All fabricated parts are sealed with a glass lid and a getter in an inert nitrogen atmosphere.
Application Example 3
Comparative Application Example 1 is repeated except that the host (CC-3) is replaced by
Figure imgf000130_0001
compound
OLED characterization
To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the light output emitted. The light output is converted to photometric parameters by calibration with a photometer. The results are shown in Table 1. Data are given at luminance (L) = 1000 Cd/m2 except otherwise stated.
Table 1
Figure imgf000130_0002
1) External quantum efficiency (EQE) is # of generated photons escaped from a substance or a device / # of electrons flowing through it.
It is evident that the EQE is increased by replacing host (CC-2) by compound (F-2) accord- ing to the present invention, which is very important property to realise high efficiency device.

Claims

Claims
1. A
Figure imgf000131_0001
(I), wherein
Y1 and Y2 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7-C2saralkyl group, which can optionally be substituted by G;
d is 0, or 1 ; c is 0, or 1 ;
R1 and R6 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by
G; or a group of formula -(AV(A2)p-(A3)q-(A4)rR16,
a is 0, 1 , 2, or 3; b is 0, 1 , 2, or 3;
o is 0, or 1 , p is 0, or 1 , q is 0, or 1 , r is 0, or 1 ,
A1, A2, A3 and A4 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, or a C2-C3oheteroarylen group, which can optionally be substituted by G;
R16 is H, -NR10R11 , or -Si(R 2)(R 3)(R14), a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
R10 and R11 are independently of each other a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
R12, R13 and R14 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR65-, -SiR70R71-, -POR72-, -CR63=CR64-, or -C≡C-,
E is -OR69, -SR69, -NR65R66, -COR68, -COOR67, -CONR65R66, -CN, or F,
G is E, or a d-dsalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by F, Ci-Ci8alkyl, or C-i-dsalkyl which is substituted by F and/or interrupted by O; a C2-C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, Ci-Ci8alkyl, -Si(R 2')(R 3')(R14'), or Ci-Ci8alkyl which is interrupted by O;
R12' R13' anc| R14' are independently of each other a Ci-C2salkyl group, which can optionally be interupted by O; a C6-Ci4arylgroup, which can optionally be substituted by Ci-Ci8alkyl ; or a C2-Cioheteroaryl group, which can optionally be substituted by Ci- Ciealkyl ; R63 and R64 are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-;
R65 and R66 are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-; or
R65 and R66 together form a five or six membered ring,
R67 is a C6-Ciearyl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-, R68 is H; a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by - 0-,
R69 is a C6-Ciearyl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-,
R70 and R71 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Ci8aryl group, which is substituted by Ci-Cisalkyl, and
R72 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, with the proviso that at least one of the substituents R1 and R6 represent a group of formula -(A1)0-(A2)p-(A3)q-(A4)rR16 and with the further proviso that R16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
2. T
Figure imgf000132_0001
wherein R1, R2, R3 and R6 are independently of each other a group of formula— (A1)0- (A2)p-(A3)q-(A4)rR16, wherein c is 0, or 1 ; d is 0, or 1 ; o, p, q, r, Y Y2, Ai, A2, A3, A4 and R16 as defined in claim 1.
3. The compound according to claim 1 , which is a compound of formula
Figure imgf000132_0002
Figure imgf000133_0001
wherein R1 , R2, R3 and R6 are independently of each other a group of formula— (A1)0- (A2)p-(A3)q-(A4)rR16, wherein o, p, q, r, A1 , A2, A3, A4 and R16 as defined in claim 1.
T 1 , which is a compound of formula
Figure imgf000133_0002
(le),
wherein R3 and R6 are independently of each other a group of formula— (A1)0-(A2)P- (A3)q-(A4)rR16, wherein c is 0, or 1 ; d is 0, or 1 ; o, p, q, r, Y1 , Y2, A1 , A2, A3, A4 and R16 as defined in claim 1.
The compound according to claim 1 , which is a compound of formula
Figure imgf000133_0003
wherein R3 and R6 are independently of each other a group of formula— (A1)0 (A3)q-(A )rR16, wherein o, p, q, r, A1 , A2, A3, A4 and R16 as defined in claim 1.
The compound according to any of claims 1 to 5, wherein A1 , A2, A3 and A4 are independently of each other a group of the formula
Figure imgf000133_0004
;wherein R89
Figure imgf000134_0001
is H, a group of formula
Figure imgf000134_0002
X is O, S, or N R24
R24 is a C6-C24aryl group, , which can optionally be substituted by G, or a C2- C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined in claim 1.
The compound according to any of claims 1 to 6, wherein R16 is H, or a group of the
f
Figure imgf000134_0003
Figure imgf000135_0001
, wherein
R12, R13 and R14 are independently of each other a phenyl group, which can optionally be substituted by one, or more Ci-Cisalkyl groups;
R21 and R21 ' are independently of each other H, a phenyl group, or a Ci-Cisalkyl group;
y of each other H, or a group of the formula
Figure imgf000135_0002
X is O, S, or NR24,
R24 is a C6-C24aryl group, , which can optionally be substituted by G, or a C2- C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined in claim 1.
The compound according to any of claims 1 to 7, wherein
o is 0, or 1 , p is 0, or 1 , q is 0, or 1 , r is 0, or 1 ,
Figure imgf000136_0001
Figure imgf000137_0001
, wherein X is O, S, or NR24, wherein
Figure imgf000138_0001
R24 is , or , with the proviso that R16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
9. The compound according to any of claims 1 to 8, wherein the group of the formula
( ,
Figure imgf000138_0002
138
Figure imgf000139_0001
Figure imgf000140_0001
140
Figure imgf000141_0001
141
Figure imgf000142_0001
Figure imgf000142_0002
Figure imgf000143_0001
(XI Vr), (XI Vs),
Figure imgf000143_0002
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000145_0002
 
Figure imgf000146_0001
(XVI lc),
Figure imgf000147_0001
(XVIIm),
Figure imgf000148_0001
Figure imgf000149_0001
5 (XVIIr),
Figure imgf000150_0001
Figure imgf000150_0002
Figure imgf000150_0003
(XVI Ix). The compound according to any of claims 1 to 8, wherein the group of the formula
Figure imgf000151_0001
(XVI I Id),
Figure imgf000152_0001
Figure imgf000152_0002
(XVIIIf),
Figure imgf000152_0003
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
represents the bonding to R16; or
R , R2, R3 and R6 are a group of formula -(A )o-(A2)p-(A3)q-(A4)rR16 , wherein -(A1)o-(A2)p-(A3)q-(A4)r is a group of formula a group of formula
Figure imgf000156_0001
Figure imgf000157_0001
Figure imgf000158_0001
T formula
Figure imgf000158_0002
R1 , R2, R3 and R6 are a group of formula -(A1)0-(A2)p-(A3)q-(A4)rR16, wherein -
Figure imgf000158_0003
(A1)o-(A2)p-(A3)q-(A4)r is a single bond, or a group of formula
Figure imgf000158_0004
Figure imgf000159_0001
a compound of formula (le'), wherein R3 and R6 are the same, or different from each other and are a group of formula -(A1)0-(A2)P- 3)q-( 4)r-R16, wherein - A1)0-(A2)p-(A3)q-(A4)r- is a single bond, or a group of for-
Figure imgf000159_0002
Figure imgf000159_0003
13. An electronic device, comprising a compound according to any of claims 1 to 12. 14. The electronic device according to claim 13, which is an electroluminescent device.
15. A charge transport layer, a charge/exciton blocker layer, or an emitting layer comprising a compound according to any of claims 1 to 12. 16. The emitting layer according to claim 15, comprising a compound according to any of claims 1 to 12 as host material in combination with a phosphorescent emitter.
17. An apparatus selected from the group consisting of stationary visual display units; mobile visual display units; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising the organic electronic device according to claim 13, or 14, or the charge transport layer, the charge/exciton blocker layer, or the emitting layer according to claim 15.
18. Use of the compounds of formula I according to any of claims 1 to 12 for electropho- tographic photoreceptors, photoelectric converters, organic solar cells, switching elements, organic light emitting field effect transistors, image sensors, dye lasers and electroluminescent devices.
PCT/EP2014/066174 2013-07-30 2014-07-28 Benzimidazolo[2,1-b][1,3]benzothiazoles for electronic applications WO2015014791A1 (en)

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