DE102012000064A1 - New heterocyclic compound excluding 9,10-dioxa-4b-aza-9a-phospha-indeno(1,2-a)indene and 9,10-dioxa-4b-aza-indeno(1,2-a)indene, useful e.g. as matrix material for fluorescent or phosphorescent emitters of electronic devices - Google Patents

Abstract

Heterocyclic compound (I) excluding 9,10-dioxa-4b-aza-9a-phospha-indeno[1,2-a]indene and 9,10-dioxa-4b-aza-indeno[1,2-a]indene, is new. Heterocyclic compound of formula (I) excluding 9,10-dioxa-4b-aza-9a-phospha-indeno[1,2-a]indene and 9,10-dioxa-4b-aza-indeno[1,2-a]indene, is new. X : C, Si, B, Al, N, P, P=O or P=S; Y1 : NA2, O or S; A1, A1+C, A2 : (hetero)aryl with 5-20 aromatic ring atoms (optionally substituted by at least one group R), where A1 and A2 may be bonded together by single bond, C(R) 2, NR, BR, O or S; either R : 2-40C alkenyl, 2-40C alkynyl (where in both groups at least one non-adjacent CH 2group may be replaced by R2C=CR2, CC, Si(R2) 2, C=O, C=S, C=NR2, P(=O)(R2), SO, SO 2, NR2, O, S or CONR2, and at least one H may be replaced by D, F, Cl, Br, I, CN or NO 2), (hetero)aromatic ring with 5-60 aromatic ring atoms, (hetero)aryloxy with 5-60 aromatic ring atoms (all optionally substituted by at least one group R2), 1-40C alkoxy, 1-40C (thio)alkyl (both linear), 3-40C alkoxy, 3-40C (thio)alkyl (both branched or cyclic), H, D, F, Cl, Br, I, CN, NO 2, N(A3) 2, N(R2) 2, C(=O)A3, C(=O)R2 and/or P(=O)(A3) 2; or at least 2R : monocyclic or polycyclic and aliphatic or (hetero)aromatic ring (optionally substituted by at least one group R2); either R1 : R or heterocyclic moiety of formula (II); or 2R1 : ring (when n = 2); L : single bond or divalent group; either R2 : 2-40C alkenyl, 2-40C alkynyl (where in both groups at least one non-adjacent CH 2group may be replaced by R3C=CR3, CC, Si(R3) 2, C=O, C=S, C=NR3, P(=O)(R3), SO, SO 2, NR3, O, S or CONR3, and at least one H may be replaced by D, F, Cl, Br, I, CN or NO 2), (hetero)aromatic ring with 5-60 aromatic ring atoms, (hetero)aryloxy with 5-60 aromatic ring atoms (all optionally substituted by at least one group R3), 1-40C alkoxy, 1-40C (thio)alkyl (both linear), 3-40C alkoxy, 3-40C (thio)alkyl (both branched or cyclic), H, D, F, Cl, Br, I, CN, NO 2, N(A3) 2, N(R3) 2, C(=O)A3, C(=O)R3 and/or P(=O)(A3) 2; or at least 2R2 : monocyclic or polycyclic and aliphatic or (hetero)aromatic ring (optionally substituted by at least one group R3); A3 : (hetero)aromatic ring with 5-30 aromatic ring atoms (optionally substituted by at least one non-aromatic group R3), where two A3, which are bonded to same N or P, are bonded together by single bond, N(R3), C(R3) 2, O or S; either R3 : (hetero)aromatic ring with 5-30 aromatic ring atoms (where at least one H may be replaced by D, F, Cl, Br, I or CN), aliphatic 1-20C hydrocarbyl, H, D, F or CN; or at least 2R3 : mono or polycyclic and aliphatic or (hetero)aromatic ring; and n : 0 (when X = B, Al, N, P=O or P=S), 1 (when X = C or Si) or 0 or 2 (when X = P). Independent claims are also included for: (1) preparing (I); and (2) an oligomer, polymer or a dendrimer comprising at least one compound (I), which comprises at least one bond of (I) to the polymer, oligomer or the dendrimer. [Image].

Description

The present invention relates to materials for use in electronic devices, in particular in organic electroluminescent devices, as well as electronic devices, in particular organic electroluminescent devices containing these materials.

The construction of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is described, for example, in US Pat US 4539507 . US 5151629 . EP 0676461 and WO 98/27136 described. In this case, increasingly, organometallic complexes which exhibit phosphorescence instead of fluorescence are used as emitting materials ( MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6 ). For quantum mechanical reasons, up to four times energy and power efficiency is possible using organometallic compounds as phosphorescence emitters. In general, OLEDs, in particular OLEDs, show triplet emission (phosphorescence) but still need to be improved, for example with regard to efficiency, operating voltage and service life. This applies in particular to OLEDs which emit in the shorter wavelength range, for example green.

The properties of phosphorescent OLEDs are not only determined by the triplet emitters used. Here, in particular, the other materials used, such as matrix materials, hole blocking materials, electron transport materials, hole transport materials and electron or exciton blocking materials are of particular importance. Improvements to these materials can thus also lead to significant improvements in the OLED properties. Even for fluorescent OLEDs there is still room for improvement with these materials.

According to the prior art, ketones (for example according to US Pat WO 2004/093207 or WO 2010/006680 ) or phosphine oxides (eg according to WO 2005/003253 ) are used as matrix materials for phosphorescent emitters. However, with the use of these matrix materials, as with other matrix materials, there is still room for improvement, particularly with regard to the efficiency and the life of the device.

According to the prior art carbazole derivatives, z. B. according to WO 2005/039246 . US 2005/0069729 . JP 2004/288381 . EP 1205527 or WO 2008/086851 , and indolocarbazole derivatives, e.g. B. according to WO 2007/063754 or WO 2008/056746 , used as matrix materials for phosphorescent emitters in organic electroluminescent devices. These are often very sensitive to oxidation, which impairs the preparation, purification and storage of the materials and the long-term stability of solutions containing the materials. Here further improvements are desirable, as well as in terms of the efficiency, lifetime and thermal stability of the materials.

The object of the present invention is to provide compounds which are suitable for use in a fluorescent or phosphorescent OLED, in particular a phosphorescent OLED, in particular as matrix material or as hole transport / electron blocking material or exciton blocking material. In particular, it is the object of the present invention to provide matrix materials which are suitable for blue, green and / or red phosphorescent OLEDs.

Surprisingly, it has been found that certain compounds described in more detail below achieve this object and lead to significant improvements in the organic electroluminescent device, in particular with regard to the service life, the efficiency and / or the operating voltage. This applies to red, green and partly also to blue phosphorescent electroluminescent devices, especially when the compounds according to the invention are used as matrix material. These compounds as well as electronic devices, in particular organic electroluminescent devices containing such compounds, are therefore the subject of the present invention.

wobei für die verwendeten Symbole und Indizes gilt:
X ist bei jedem Auftreten gleich oder verschieden C, Si, B, Al, N, P, P=O oder P=S;
Y ist bei jedem Auftreten gleich oder verschieden NAr², O oder S;
Ar¹ ist bei jedem Auftreten gleich oder verschieden zusammen mit den explizit dargestellten Kohlenstoffatomen eine Aryl- oder Heteroarylgruppe mit 5 bis 20 aromatischen Ringatomen, die mit einem oder mehreren Resten R substituiert sein kann;
Ar² ist bei jedem Auftreten gleich oder verschieden eine Aryl- oder Heteroarylgruppe mit 5 bis 20 aromatischen Ringatomen, die mit einem oder mehreren Resten R substituiert sein kann;
dabei können benachbarte Gruppen Ar¹ und Ar² auch durch eine Einfachbindung oder durch eine Gruppe, ausgewählt aus CR₂, NR, BR, O oder S, miteinander verknüpft sein;
R ist bei jedem Auftreten gleich oder verschieden ausgewählt aus der Gruppe bestehend aus H, D, F, Cl, Br, I, CN, NO₂, N(Ar³)₂, N(R²)₂, C(=O)Ar³, C(=O)R², P(=O)(Ar³)₂, einer geradkettigen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 40 C-Atomen oder einer verzweigten oder cyclischen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 40 C-Atomen oder einer Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R² substituiert sein kann, wobei eine oder mehrere nicht-benachbarte CH₂-Gruppen durch R²C=CR², C≡C, Si(R²)₂, C=O, C=S, C=NR², P(=O)(R²), SO, SO₂, NR², O, S oder CONR² ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, einem aromatischen oder heteroaromatischen Ringsystem mit 5 bis 60, aromatischen Ringatomen, das jeweils mit einem oder mehreren Resten R² substituiert sein kann, einer Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die mit einem oder mehreren Resten R² substituiert sein kann, oder einer Kombination dieser Systeme, wobei optional zwei oder mehr benachbarte Substituenten R ein monocyclisches oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden können, das mit einem oder mehreren Resten R² substituiert sein kann;
R¹ ist bei jedem Auftreten gleich oder verschieden R oder eine Gruppe der folgenden Formel (2),

wobei die verwendeten Symbole die gleiche Bedeutung aufweisen, wie für Formel (1) beschrieben, die gestrichelte Bindung die Bindung an X andeutet und L für eine Einfachbindung oder eine bivalente Gruppe steht;
dabei können zwei Gruppen R¹, wenn n = 2 ist, auch miteinander einen Ring bilden;
R² ist bei jedem Auftreten gleich oder verschieden ausgewählt aus der Gruppe bestehend aus H, D, F, Cl, Br, I, CN, NO₂, N(Ar³)₂, N(R³)₂, C(=O)Ar³, C(=O)R³, P(=O)(Ar³)₂, einer geradkettigen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 1 bis 40 C-Atomen oder einer verzweigten oder cyclischen Alkyl-, Alkoxy- oder Thioalkylgruppe mit 3 bis 40 C-Atomen oder einer Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R³ substituiert sein kann, wobei eine oder mehrere nicht-benachbarte CH₂-Gruppen durch R³C=CR³, C≡C, Si(R³)₂, C=O, C=S, C=NR³, P(=O)(R³), SO, SO₂, NR³, O, S oder CONR³ ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, einem aromatischen oder heteroaromatischen Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils mit einem oder mehreren Resten R³ substituiert sein kann, einer Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die mit einem oder mehreren Resten R³ substituiert sein kann, oder einer Kombination dieser Systeme, wobei optional zwei oder mehr benachbarte Substituenten R² ein monocyclisches oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden können, das mit einem oder mehreren Resten R³ substituiert sein kann;
Ar³ ist bei jedem Auftreten gleich oder verschieden ein aromatisches oder heteroaromatisches Ringsystem mit 5–30 aromatischen Ringatomen, das mit einem oder mehreren nicht-aromatischen Resten R³ substituiert sein kann; dabei können zwei Reste Ar², welche an dasselbe N-Atom oder P-Atom binden, auch durch eine Einfachbindung oder eine Brücke, ausgewählt aus N(R³), C(R³)₂, O oder S, miteinander verbrückt sein;
R³ ist bei jedem Auftreten gleich oder verschieden ausgewählt aus der Gruppe bestehend aus H, D, F, CN, einem aliphatischen Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, einem aromatischen oder heteroaromatischen Ringsystem mit 5 bis 30 aromatischen Ringatomen, in dem ein oder mehrere H-Atome durch D, F, Cl, Br, I oder CN ersetzt sein können, wobei zwei oder mehr benachbarte Substituenten R³ miteinander ein mono- oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden können;
ist 0, wenn X für B, Al, N, P=O oder P=S steht, und ist 1, wenn X für C oder Si steht, und ist 0 oder 2, wenn X für P steht;
dabei sind die folgenden Verbindungen von der Erfindung ausgenommen:

The present invention relates to a compound according to the following formula (1)

where the symbols and indices used are:
X is the same or different at each occurrence, C, Si, B, Al, N, P, P = O or P = S;
Y is the same or different NAr ² , O or S at each occurrence;
Ar ¹ at each occurrence, identically or differently together with the explicitly illustrated carbon atoms, is an aryl or heteroaryl group having 5 to 20 aromatic ring atoms which may be substituted by one or more radicals R;
Ar ² is the same or different at each occurrence and is an aryl or heteroaryl group having 5 to 20 aromatic ring atoms which may be substituted by one or more R radicals;
adjacent groups Ar ¹ and Ar ^{2 may} also be linked together by a single bond or by a group selected from CR ₂ , NR, BR, O or S;
R is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (Ar ³ ) ₂ , N (R ² ) ₂ , C (= O) Ar ³ , C (= O) R ² , P (= O) (Ar ³ ) ₂ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted with one or more R ² radicals, wherein one or more non-adjacent CH ₂ groups is represented by R ² C = CR ² , C≡C, Si (R ² ) ₂ , C =O, C =S, C =NR ² , P (= O) (R ² ), SO, SO ₂ , NR ² , O, S or CONR ² and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, each containing one or more Radicals R ² may be substituted, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ² , or a combination of these systems, wherein optionally two or more adjacent substituents R is a monocyclic or may form a polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R ² radicals;
R ¹ is the same or different at each occurrence R or a group of the following formula (2),

wherein the symbols used have the same meaning as described for formula (1), the dashed bond indicates bonding to X and L is a single bond or a divalent group;
two groups R ¹ , if n = 2, can also form a ring with each other;
R ² is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (Ar ³ ) ₂ , N (R ³ ) ₂ , C (= O ) Ar ³ , C (= O) R ³ , P (= O) (Ar ³ ) ₂ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or Thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more radicals R ³ , wherein one or more non-adjacent CH ₂ groups by R ³ C = CR ³ , C≡C, Si (R ³ ) ₂ , C =O, C =S, C =NR ³ , P (= O) (R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each with one or more R ³ may be substituted, an aryloxy or heteroaryloxy group having 5 to 60 aromatisc hen ring atoms, which may be substituted by one or more radicals R ³ , or a combination of these systems, wherein optionally two or more adjacent substituents R ^{2 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system having one or more radicals R ³ may be substituted;
Ar ³ is the same or different at each occurrence, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which may be substituted with one or more non-aromatic radicals R ³ ; two Ar ² radicals which bind to the same N atom or P atom may also be bridged together by a single bond or a bridge selected from N (R ³ ), C (R ³ ) ₂ , O or S;
R ³ in each occurrence is identically or differently selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or multiple H atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R ^{3 may form} together a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
is 0 when X is B, Al, N, P = O or P = S, and is 1 when X is C or Si, and is 0 or 2 when X is P;
the following compounds are excluded from the invention:

Among adjacent groups Ar ¹ and Ar ² , which may be linked together, it is understood that the symbol Y which binds the corresponding group Ar ¹ stands for NAr ² and that this group Ar ^{2 is} linked to the corresponding group Ar ¹ , this linkage being via a single bond or via the groups listed above, ie via CR ₂ , NR, BR, O or S.

An aryl group in the sense of this invention contains 6 to 60 C atoms; For the purposes of this invention, a heteroaryl group contains 2 to 60 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms gives at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, under an aryl group or heteroaryl either a simple aromatic cycle, ie benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a fused (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc., understood. By contrast, aromatics linked to one another by single bond, such as, for example, biphenyl, are not designated as aryl or heteroaryl group but as aromatic ring system.

An aromatic ring system in the sense of this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 2 to 60 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms gives at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the sense of this invention is to be understood as meaning a system which does not necessarily contain only aryl or heteroaryl groups but in which also several aryl or heteroaryl groups a non-aromatic moiety, such as As a C, N or O atom can be connected. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are to be understood as aromatic ring systems in the context of this invention, and also systems in which two or more aryl groups, for example are linked by a short alkyl group.

In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 40 C atoms, and in which also individual H atoms or CH ₂ groups, may be represented by the abovementioned groups Preferably, the radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl , Cyclopentyl, n-hexyl, neo -hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl , Hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. Among an alkoxy group having 1 to 40 carbon atoms, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy understood. In particular, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-butylthio, n-butylthio, n-butylthio, n-butylthio Hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2- Trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkyl groups according to the present invention may be straight-chain, branched or cyclic, wherein one or more non-adjacent CH ₂ groups may be replaced by the above-mentioned groups; Furthermore, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN or NO ₂ , preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

Under an aromatic or heteroaromatic ring system with 5-60 aromatic ring atoms, which may be substituted in each case with the above-mentioned radicals R ² or a hydrocarbon radical and which may be linked via any position on the aromatic or heteroaromatic, are understood in particular groups derived are benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene , cis or trans indenocarbazole, cis or trans indolocarbazole, Truxen, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline , Isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, Be nzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4, 5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1, 2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or groups derived from combination of these systems.

In a preferred embodiment of the invention, X is the same or different at each occurrence as Si, B, P, P =O or N, particularly preferably Si, P or P =O.

In a further preferred embodiment of the invention, Y is identical or different at each occurrence for NAr ² or O, particularly preferably for NAr ² .

More preferably, X is the same or different each occurrence of Si, B, P, P = O or N and Y is the same or different at each occurrence for NAr ² or O. Most preferably, X is the same or different at each occurrence Si, P or P = O and Y is NAr ² .

Furthermore, all groups Y are preferably chosen the same.

In a preferred embodiment of the invention, Ar ^{1 is the} same or different at each occurrence as an aryl group having 6 to 10 aromatic carbon atoms which may be substituted by one or more R groups, or a heteroaryl group having 5 to 13 aromatic ring atoms substituted with a or a plurality of R may be substituted.

wobei # die Position der Verknüpfung mit Y andeutet, * die Position der Verknüpfung mit dem Stickstoffatom andeutet und weiterhin gilt:
W ist gleich oder verschieden bei jedem Auftreten CR oder N; oder zwei benachbarte Gruppen W stehen für eine Gruppe der folgenden Formel (8) oder (9),

wobei V für NR, O oder S steht, Z gleich oder verschieden bei jedem Auftreten für CR oder N steht und ^ die entsprechenden benachbarten Gruppen W in der Formel (3) bis (7) andeuten.In a particularly preferred embodiment of the invention, the group Ar ^{1 is,} identically or differently on each occurrence, a group of the following formula (3), (4), (5), (6) or (7),

where # indicates the position of the linkage with Y, * indicates the position of the linkage with the nitrogen atom, and furthermore:
W is the same or different every occurrence CR or N; or two adjacent groups W stand for a group of the following formula (8) or (9),

wherein V is NR, O or S, Z is the same or different at each occurrence is CR or N and ^ indicate the corresponding adjacent groups W in the formula (3) to (7).

In a preferred embodiment of the invention, the group of the formula (3) is benzene, pyridine, pyrimidine, pyridazine or pyrazine, which may each be substituted by one or more radicals R.

In a particularly preferred embodiment of the invention, Ar ^{1 represents} a group of the abovementioned formula (3), where adjacent groups W do not stand for a group of the formula (8) or (9). In the group of formula (3), all symbols W are preferably CR.

wobei die verwendeten Symbole und Indizes die oben genannten Bedeutungen aufweisen.Preferred compounds of the formula (1) are therefore the compounds of the following formula (10),

wherein the symbols and indices used have the meanings given above.

wobei die verwendeten Symbole und Indizes die oben genannten Bedeutungen aufweisen.A preferred embodiment of the compounds of the formula (10) are the compounds of the following formula (10a)

wherein the symbols and indices used have the meanings given above.

In a further preferred embodiment of the invention, Ar ^{2 is the} same or different at each occurrence as an aryl group having 6 to 10 aromatic carbon atoms which may be substituted by one or more R groups, or a heteroaryl group having 5 to 13 aromatic ring atoms substituted with one or more radicals R may be substituted. Particularly preferred Ar ² groups are selected from benzene, 1- or 2-naphthalene, pyrrole, furan, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, benzofuran, benzothiophene, indole, dibenzofuran, dibenzothiophene and carbazole, or combinations of these radicals each may be substituted by one or more radicals R.

Preferred radicals R which bind to Ar ² are H and aromatic ring systems. Particularly preferred groups R ² substituted by R are benzene, biphenyl, ortho-, meta- or para-terphenyl or ortho, meta, para or branched quaterphenyl and also pyrimidine, phenylpyrimidine, diphenylpyrimidine, 1,3,5-triazine and diphenyl triazine -1,3,5-.

wobei die verwendeten Symbole und Indizes die oben genannten Bedeutungen aufweisen und E gleich oder verschieden bei jedem Auftreten für eine Einfachbindung, CR₂, NR, BR, O oder S steht. Dabei ist Ar² jeweils in ortho-Position mit N und E verknüpft. As described above, adjacent groups Ar ¹ and Ar ^{2 may} be linked together by a single bond or a group selected from CR ₂ , NR, BR, O or S. Such compounds are represented by the following formulas (11) and (12):

where the symbols and indices used have the abovementioned meanings and E is the same or different at each occurrence as a single bond, CR ₂ , NR, BR, O or S. Ar ² is linked to N and E in the ortho position.

wobei die verwendeten Symbole und Indizes die oben genannten Bedeutungen aufweisen.Preferred embodiments of the formulas (11) and (12) are the compounds of the following formulas (11a) and (12a),

wherein the symbols and indices used have the meanings given above.

Particularly preferred embodiments of the formulas (11a) and (12a) are compounds in which Ar ^{2 is} an ortho-phenyl group which may be substituted by one or more radicals R.

Further preferred embodiments of the formulas (11) and (11a) are compounds in which Y is NAr ² or O, in particular NAr ² .

When R ^{1 is} a group of the formula (2), L is preferably selected from a single bond, O, S, NR, PR, P (= O) R, SiR ₂ , BR, an alkylene group having 1 to 10 C atoms which may also be substituted by one or more radicals R, or a bivalent aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R.

In a preferred embodiment of the invention, R, in particular R, which binds to Ar ¹ in the abovementioned formulas is the same or different at each occurrence selected from the group consisting of H, D, F, Cl, Br, CN, N (Ar ³ ) ₂ , C (= O) Ar ³ , a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms, each of which may be substituted by one or more R ² radicals, wherein one or more non-adjacent CH ₂ groups may be replaced by O and wherein one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R ² radicals, or a combination of these systems.

In a particularly preferred embodiment of the invention, R in the abovementioned formulas is the same or different at each occurrence selected from the group consisting of H, D, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more R ² radicals, wherein one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic Ring system having 5 to 18 aromatic ring atoms, each of which may be substituted by one or more R ² radicals, or a combination of these systems.

In this case, for compounds which are processed by vacuum evaporation, the alkyl groups preferably have not more than five carbon atoms, more preferably not more than 4 carbon atoms, most preferably not more than 1 carbon atom. For compounds which are processed from solution, compounds which are substituted by alkyl groups having up to 10 carbon atoms or are substituted with oligoarylene groups, for example ortho, meta, para or branched terphenyl or quaterphenyl groups, are also suitable.

The above-mentioned preferred embodiments can be arbitrarily combined with each other. In a particularly preferred embodiment of the invention, the abovementioned preferences occur simultaneously.

When the compounds of the formula (1) or the preferred embodiments are used as the electron transport material, it is preferred if the group X is B, Si or P = O and / or if at least one of the radicals R and / or Ar ^{2 is} an electron-deficient heteroaromatic ring system is. Low-electron heterocycles according to the invention are five-membered heterocycles having at least two heteroatoms or six-membered heterocycles, to each of which one or more aromatic or heteroaromatic groups may be fused, such as substituted or unsubstituted imidazoles, pyrazoles, thiazoles, oxazoles, oxadiazoles, triazoles, pyridines, pyrazines, pyrimidines , Pyridazines, triazines, imidazoles, etc ..

When the compounds of the formula (1) or the preferred embodiments are used as the matrix material for a phosphorescent emitter, it is preferred that the group X is P, P = O or Si and when the radicals R and Ar ^{2 are} not condensed aryl - or heteroaryl contain in which more than two six-membered rings are condensed directly to each other. In particular, it is preferred if the radicals R and Ar ² do not contain a fused aryl or heteroaryl group in which two or more six-membered rings are directly fused to one another.

When the compounds of the formula (1) or the preferred embodiments are used as the hole transport material, it is preferable that the group X is N, P or Si. Furthermore, it is preferred if one or more substituents R contain aromatic amines, such as, for example, diarylamino or triarylamino groups.

Examples of preferred compounds according to the above-mentioned embodiments are the compounds of the following structures 1 to 74.

The compounds of the formula (1) or the preferred embodiments can be prepared by synthesis steps known to the person skilled in the art (Scheme 1). Instead of the phenylamines shown, other aromatic or heteroaromatic amines can be used quite analogously. Scheme 1:

According to the process shown in Scheme 2, unsymmetrical triamines can be prepared, which can then be converted into the corresponding unsymmetrical compounds of the invention as described in Scheme 1. Scheme 2:

According to the method shown in Scheme 3, the compounds of the invention can be prepared with NNO coordination. Scheme 3:

According to the method shown in Scheme 4, the compounds of the invention can be prepared with ONO coordination. Scheme 4:

• a) Darstellung eines Triamins, eines Diaminoalkohols bzw. eines Aminodialkohols;
• b) dreifache Deprotonierung des Triamins, Diaminoalkohols bzw. Aminodialkohols mit einer Base; und
• c) Umsetzung des deprotonierten Triamins, des deprotonierten Diaminoalkohols bzw. des deprotonierten Aminodialkohols mit einem Elektrophil, das drei Abgangsgruppen trägt.

Another object of the present invention is therefore a process for the preparation of a compound according to formula (1), comprising the reaction steps:

• a) Preparation of a triamine, a diamino alcohol or an aminodialcohol;
• b) triple deprotonation of the triamine, diamino alcohol or aminodialcohol with a base; and
• c) Reaction of the deprotonated triamine, the deprotonated diaminoalcohol or the deprotonated aminodialcohol with an electrophile carrying three leaving groups.

The compounds according to the invention described above, in particular compounds which are substituted with reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid esters, or with reactive, polymerizable groups, such as olefins or oxetanes, can be used as monomers for producing corresponding oligomers, dendrimers or Find polymer use. The oligomerization or polymerization is preferably carried out via the halogen functionality or the boronic acid functionality or via the polymerizable group. It is also possible to crosslink the polymers via such groups. The compounds of the invention and polymers can be used as a crosslinked or uncrosslinked layer.

The invention therefore further oligomers, polymers or dendrimers containing one or more of the compounds of the invention listed above, wherein one or more bonds of the inventive compound to the polymer, oligomer or dendrimer are present. Depending on the linkage of the compound according to the invention, this therefore forms a side chain of the oligomer or polymer or is linked in the main chain. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers may be linear, branched or dendritic. The repeat units of the compounds according to the invention in oligomers, dendrimers and polymers have the same preferences as described above.

To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Preference is given to homopolymers or copolymers in which the units of the formula (1 ') or the preferred embodiments described above are present at 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer backbone are selected from fluorene (e.g. EP 842208 or WO 2000/22026 ), Spirobifluorenes (eg according to EP 707020 . EP 894107 or WO 2006/061181 ), Para-phenylenes (e.g. WO 92/18552 ), Carbazoles (eg according to WO 2004/070772 or WO 2004/113468 ), Thiophenes (eg according to EP 1028136 ), Dihydrophenanthrenes (e.g. WO 2005/014689 ), cis and trans indenofluorenes (eg according to WO 2004/041901 or WO 2004/113412 ), Ketones (eg according to WO 2005/040302 ), Phenanthrenes (eg according to WO 2005/104264 or WO 2007/017066 ) or several of these units. The polymers, oligomers and dendrimers may also contain other units, for example hole transport units, in particular those based on triarylamines, and / or electron transport units. In addition, the polymers may either be copolymerized or mixed in as a blend containing triplet emitters. Especially the combination of units according to formula (1) or the above-described preferred embodiments with triplet emitters leads to particularly good results.

Furthermore, the compounds according to formula (1) or the above-described preferred embodiments can also be further functionalized and thus converted to extended structures. Here is an example of the reaction with arylboronic acids according to Suzuki or with primary or secondary amines according to Hartwig-Buchwald mentioned. Thus, the compounds of the formula (1) or the above-described preferred embodiments can also be bound directly to phosphorescent metal complexes or to other metal complexes.

The compounds according to the invention are suitable for use in an electronic device, in particular in an organic electroluminescent device.

Another object of the present invention is therefore the use of a compound of the invention in an electronic device, in particular in an organic electroluminescent device.

Yet another object of the present invention is an electronic device containing at least one compound of the invention.

The electronic device according to the present invention is a device which contains at least one layer containing at least one organic compound. However, the component may also contain inorganic materials or even layers which are completely composed of inorganic materials.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors ( O-LETs), organic solar cells (O-SCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O Laser) and "organic plasmon emitting devices" ( Koller et al., Nature Photonics 2008, 1-4 ), but preferably organic electroluminescent devices (OLEDs), particularly preferably phosphorescent OLEDs.

The organic electroluminescent device includes cathode, anode and at least one emitting layer. In addition to these layers, they may also contain further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers. Likewise, interlayer may be introduced between two emitting layers which, for example, have an exciton-blocking function. It should be noted, however, that not necessarily each of these layers must be present. In this case, the organic electroluminescent device may contain an emitting layer, or it may contain a plurality of emitting layers. If several emission layers are present, they preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, so that overall white emission results, ie in the emitting layers different emitting compounds are used, which can fluoresce or phosphoresce. Especially preferred are systems with three emitting layers, wherein the three layers blue, green and orange or red emission show (for the basic structure, see for example WO 2005/011013 ).

The compound of the invention according to the embodiments listed above can be used in different layers, depending on the exact structure. Preference is given to an organic electroluminescent device comprising a compound according to formula (1) or the preferred embodiments described above as matrix material for fluorescent or phosphorescent emitters, in particular for phosphorescent emitters, and / or in a hole blocking layer and / or in an electron transport layer and / or in an electron-blocking or exciton-blocking layer and / or in a hole transport layer, depending on the exact substitution.

In a further embodiment of the invention, the organic electroluminescent device contains the compound according to formula (1) or the above-described preferred embodiments in an optical coupling-out layer. An optical coupling-out layer is understood to be a layer which does not lie between the anode and the cathode, but which is applied to an electrode outside the actual device, for example between an electrode and a substrate, in order to improve the optical coupling-out.

In a preferred embodiment of the invention, the compound according to formula (1) or the above-described preferred embodiments is used as matrix material for a fluorescent or phosphorescent compound, in particular for a phosphorescent compound, in an emitting layer. In this case, the organic electroluminescent device may contain an emitting layer, or it may contain a plurality of emitting layers, wherein at least one emitting layer contains at least one compound according to the invention as matrix material.

When the compound according to formula (1) or the preferred embodiments outlined above is used as the matrix material for an emitting compound in an emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). In the context of this invention, phosphorescence is understood as meaning the luminescence from an excited state with a higher spin multiplicity, ie a spin state> 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes are to be regarded as phosphorescent compounds.

The mixture of the compound according to formula (1) or the above-described preferred embodiments and the emitting compound contains between 99 and 1 vol.%, Preferably between 98 and 10 vol.%, Particularly preferably between 97 and 60 vol. %, in particular between 95 and 80 vol .-% of the compound according to formula (1) or the above-described preferred embodiments based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 1 and 99% by volume, preferably between 2 and 90% by volume, more preferably between 3 and 40% by volume, in particular between 5 and 20% by volume of the emitter, based on the total mixture Emitter and matrix material.

A further preferred embodiment of the present invention is the use of the compound of the formula (1) or of the above-described preferred embodiments as a matrix material for a phosphorescent emitter in combination with another matrix material. Particularly suitable matrix materials which can be used in combination with the compounds according to formula (1) or the above-described preferred embodiments are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, eg. B. according to WO 2004/013080 . WO 2004/093207 . WO 2006/005627 or WO 2010/006680 , Triarylamines, carbazole derivatives, e.g. B. CBP (N, N-bis-carbazolylbiphenyl) or in WO 2005/039246 . US 2005/0069729 . JP 2004/288381 . EP 1205527 or WO 2008/086851 disclosed carbazole derivatives, indolocarbazole derivatives, e.g. B. according to WO 2007/063754 or WO 2008/056746 , Indenocarbazole derivatives, e.g. B. according to WO 2010/136109 or WO 2011/000455 , Azacarbazolderivate, z. B. according to EP 1617710 . EP 1617711 . EP 1731584 . JP 2005/347160 , bipolar matrix materials, e.g. B. according to WO 2007/137725 , Silane, z. B. according to WO 2005/111172 , Azaborole or Boronester, z. B. according to WO 2006/117052 , Triazine derivatives, e.g. B. according to WO 2007/063754 . WO 2008/056746 . WO 2010/015306 . WO 2011/057706 . WO 2011/060859 or WO 2011/060877 , Zinc complexes, e.g. B. according to EP 652273 or WO 2009/062578 , Diazasilal- or tetraazasilol derivatives, z. B. according to WO 2010/054729 , Diazaphosphole derivatives, e.g. B. according to WO 2010/054730 , bridged carbazole derivatives, eg. B. according to WO 2011/042107 . WO 2011/060867 and WO 2011/088877 , Likewise, a further phosphorescent emitter, which emits shorter wavelength than the actual emitter, may be present as a co-host in the mixture.

Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds which emit light, preferably in the visible range, when suitably excited, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferred phosphorescence emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum.

Examples of the emitters described above can be found in the applications WO 00/70655 . WO 2001/41512 . WO 2002/02714 . WO 2002/15645 . EP 1191613 . EP 1191612 . EP 1191614 . WO 2005/033244 . WO 2005/019373 . US 2005/0258742 and WO 2010/086089 be removed. In general, all phosphorescent complexes used in the prior art for phosphorescent OLEDs and as known to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art may use other phosphorescent complexes without inventive step.

In a further embodiment of the invention, the organic electroluminescent device according to the invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, ie the emitting layer directly adjoins the hole injection layer or the anode, and / or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, such as in WO 2005/053051 described. Furthermore, it is possible to use a metal complex, which is the same or similar to the metal complex in the emitting layer, directly adjacent to the emitting layer as a hole-transporting or hole-injection material, such as. In WO 2009/030981 described.

In a further preferred embodiment of the invention, the compound according to formula (1) or the above-described preferred embodiments is used as an electron transport material in an electron transport or electron injection layer. In this case, the emitting layer may be fluorescent or phosphorescent. When the compound is used as an electron transport material, it may be preferred if it is doped, for example, with alkali metal complexes, such as. B. LiQ (Lithiumhydroxychinolinat).

In yet another preferred embodiment of the invention, the compound according to formula (1) or the above-described preferred embodiments is used in a hole blocking layer. A hole blocking layer is understood as meaning a layer which directly adjoins an emitting layer on the cathode side.

It is further possible to use the compound according to formula (1) or the preferred embodiments outlined above both in a hole-blocking layer or electron-transport layer and as a matrix in an emitting layer.

In yet a further embodiment of the invention, the compound according to formula (1) or the above-described preferred embodiments is used in a hole transport layer or in an electron blocking layer or exciton blocking layer.

In the further layers of the organic electroluminescent device according to the invention, it is possible to use all the materials conventionally used according to the prior art. The person skilled in the art can therefore use, without inventive step, all materials known for organic electroluminescent devices in combination with the compounds according to the invention of formula (1) or the preferred embodiments described above.

Further preferred is an organic electroluminescent device, characterized in that one or more layers are coated with a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. But it is also possible that the initial pressure is even lower, for example less than 10 ^-7 mbar.

Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated with the OVPD (Organic Vapor Phase Deposition) method or with the aid of a carrier gas sublimation. The materials are applied at a pressure between 10 ^-5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (eg. MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301 ).

Further preferred is an organic electroluminescent device, characterized in that one or more layers of solution, such. B. by spin coating, or with any printing process, such. As screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), ink-jet printing (ink jet printing) or Nozzle Printing, are produced. For this purpose, soluble compounds are necessary, which are obtained for example by suitable substitution.

Furthermore, hybrid processes are possible in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

These methods are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

• 1. Die erfindungsgemäßen Verbindungen bzw. Verbindungen gemäß Formel (1) bzw. die oben ausgeführten bevorzugten Ausführungsformen, eingesetzt als Matrixmaterial für fluoreszierende oder phosphoreszierende Emitter, führen zu sehr hohen Effizienzen sowie zu langen Lebensdauern. Dies gilt insbesondere, wenn die Verbindungen als Matrixmaterial für einen phosphoreszierenden Emitter eingesetzt werden.
• 2. Die erfindungsgemäßen Verbindungen bzw. Verbindungen gemäß Formel (1) bzw. die oben ausgeführten bevorzugten Ausführungsformen eignen sich nicht nur als Matrix für rot phosphoreszierende Verbindungen, sondern auch für grün und gegebenenfalls auch für blau phosphoreszierende Verbindungen.

The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished by the following surprising advantages over the prior art:

• 1. The compounds according to the invention or compounds of the formula (1) or the above-described preferred embodiments, used as a matrix material for fluorescent or phosphorescent emitters, lead to very high efficiencies and to long lifetimes. This applies in particular if the compounds are used as matrix material for a phosphorescent emitter.
• 2. The compounds of the invention or compounds of formula (1) or the above-described preferred embodiments are not only suitable as a matrix for red phosphorescent compounds, but also for green and optionally also for blue phosphorescent compounds.

These advantages mentioned above are not accompanied by a deterioration of the other electronic properties.

The invention is explained in more detail by the following examples without wishing to restrict them thereby. The person skilled in the art can, from the descriptions, carry out the invention in the entire disclosed area and produce other inventive compounds without inventive step and use them in electronic devices or use the method according to the invention.

Examples:

Unless stated otherwise, the following syntheses are carried out under an inert gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers given for the non-commercially available educts are the corresponding CAS numbers.

Example 1: Bis- (4- (3-phenylamino)) biphenyl) amine

A) Bis (4- (3-bromobiphenyl)) amine

A solution of 32.1 g (100 mmol) of bis (4-biphenyl) amine in 1000 ml of THF is added dropwise at 10 ° C. with stirring to a solution of 38.3 g (215 mmol) of NBS in 500 ml of THF Does not exceed 20 ° C. After completion of the addition, the mixture is stirred for 3 h at room temperature, the THF is removed in vacuo, the residue is taken up in 500 ml of ethyl acetate, the organic phase washed five times with 300 ml of water, once with 300 ml of saturated brine and dried over magnesium sulfate. After removal of the ethyl acetate in vacuo, the oily residue is recrystallized from ethanol, optionally with the addition of a little ethyl acetate. Yield: 41.7 g (87 mmol), 87%; Purity: about 99% n. NMR. B) bis (4- (3-phenylamino) biphenyl)) amine

500 ml of toluene with 3 ml (3 mmol) of tri-tert-butylphosphine (1 M in toluene), 500 mg (2 mmol) of palladium (II) acetate and after 5 min. Stir with 47.9 g (100 mmol) of bis (4- (3-bromobiphenyl)) amine, 20.5 g (220 mmol) of aniline and 33.6 g (350 mmol) of sodium tert-butoxide and heated under reflux for 6 h. After cooling, 150 ml of saturated ammonium chloride solution and 40 ml of glacial acetic acid are added, the aqueous phase is separated off, the organic phase is washed twice with 150 ml of saturated common salt, dried over magnesium sulfate, the toluene is removed in vacuo and the remaining oil is crystallized from about 100 ml of methanol. Yield: 40.3 g (80 mmol), 80%; Purity: about 98% n. NMR.

Example 2 General Synthesis Instructions

Beispiel 18: Bis(2-hydroxy-4-phenyl-phenyl)amin

a) Bis(2-hydroxy-4-bromphenyl)amin

A solution of 50.3 g (100 mmol) of bis (4- (3-phenylamino) biphenyl)) amine in 500 ml of diethyl ether is added dropwise while stirring at room temperature with 84.0 ml (210 mmol) of n-butyllithium (2.5 M in hexane). added that the temperature does not exceed 30 ° C. After completion of the addition, the mixture is stirred for a further 1 h, then added dropwise to a solution of 100 mmol of the corresponding electrophile in 200 ml of diethyl ether and stirred for 12 h at room temperature. The diethyl ether is removed in vacuo, 200 ml of methanol are added, the mixture is stirred hot, filtered off with suction, the solid is washed twice with 100 ml of methanol each time and dried in vacuo. The solid is taken up in 500 ml of dichloromethane, filtered through Alox (basic, activity level 1), the solid obtained after stripping off the dichloromethane is recrystallised three times from toluene / ethanol and finally sublimated twice in fractionated high vacuum. Purity: 99.7-99.9% by HPLC.

Example 18: Bis (2-hydroxy-4-phenylphenyl) amine

a) Bis (2-hydroxy-4-bromophenyl) amine

A solution of 20.1 g (100 mmol) of bis (2-hydroxyphenyl) amine [2391-71-1] in 1000 ml of carbon tetrachloride is added dropwise with exclusion of light at 10 ° C for 1 h with a mixture of 10.2 ml (200 mmol) of bromine and 100 ml carbon tetrachloride added and stirred for 5 h. The reaction mixture is mixed with 300 ml of saturated sodium bisulfite solution, stirred for a short time, and the organic phase is separated off, washed this once with 300 ml of saturated sodium bicarbonate solution, once with 500 ml of water and dried over sodium sulfate. The carbon tetrachloride is removed in vacuo, 100 ml of methanol are added, the mixture is stirred hot, filtered off with suction, and the solid is washed twice with 30 ml of methanol each time and dried in vacuo. The resulting solid is recrystallized twice from n-butanol. Yield: 20.1 g (56 mmol), 56%; Purity: about 98% after ¹ H-NMR.

b) Bis (2-hydroxy-4-phenylphenyl) amine

A mixture of 17.6 g (50 mmol) of bis (2-hydroxy-4-bromophenyl) amine, 15.9 g (130 mmol) of phenylboronic acid, 42.5 g (200 mmol) of tripotassium phosphate, 1.8 g (6 mmol) of tri-o-tolylphosphine, 224 mg (1 mmol) of palladium (II) acetate, 200 ml of toluene, 100 ml of dioxane and 300 ml of water is heated with good stirring for 12 h under reflux. After cooling, 40 ml of glacial acetic acid are added, the organic phase is separated, filtered through a silica gel bed (3 cm), washed twice with 200 ml of toluene and the toluene removed in vacuo. The residue is recrystallized twice from DMF / MeOH. Yield: 12.0 g (34 mmol), 68%; Purity: about 99% after ¹ H NMR.

The following compounds are obtained analogously

Example 22: General Method of Synthesis

A solution of 100 mmol of the corresponding bis (2-hydroxyphenyl) amine according to Example 18-21 in 500-1000 ml of diethyl ether is added dropwise while stirring at room temperature with 84.0 ml (210 mmol) of n-butyllithium (2.5 M in hexane). added that the temperature does not exceed 30 ° C. After completion of the addition, the mixture is stirred for a further 1 h, then added dropwise to a solution of 100 mmol of the corresponding electrophile in 200 ml of diethyl ether and stirred for 12 h at room temperature. The diethyl ether is removed in vacuo, 200 ml of methanol are added, the mixture is stirred hot, filtered off with suction, the solid is washed twice with 100 ml of methanol each time and dried in vacuo. The solid is taken up in 500 ml of dichloromethane, filtered through Alox (basic, activity level 1), the solid obtained after stripping off the dichloromethane is recrystallised three times from toluene / ethanol and finally sublimated twice in fractionated high vacuum. Purity: 99.7-99.9% by HPLC.

Example 28: Preparation and Characterization of Organic Electroluminescent Devices

Inventive electroluminescent devices can, such as. In WO 2005/003253 generally described. Here the results of different OLEDs are compared. The basic structure, the materials used, the degree of doping and their layer thicknesses are identical for better comparability.

OLEDs with the compounds 3, 4, 6 and 8 according to the invention as host material in a mixed host system with host 1 in the following layer structure are described: Hole injection layer (HIL) 20 nm of 2,2 ', 7,7'-tetrakis (di-para-tolylamino) spiro-9,9'-bifluorene Hole transport layer (HTL) 5 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl) Electron blocking layer (EBL) 15 nm EBL (9,9-bis (3,5-diphenylaminophenyl) fluorene) Emission layer (EML): 40 nm host: see Table 1, proportions in% by volume Dopant: 10 vol.% Doping, fac-tris (2-phenylpyridine) iridium (IrPPy) or Tris (1-phenylisoquinoline) iridium (IrPIQ) or fac-tris (2- (4-cyano-5-fluorophenylpyridine) iridium (IrF-CN-PPy) Electron conductor (ETL) 20 nm BAlq cathode 1 nm LiF, then 100 nm Al.

The structures of EBL and the dopants are shown below for the sake of clarity.

To characterize these OLEDs, the electroluminescence spectra, the external quantum efficiency (measured in%) as a function of the brightness, calculated from current-voltage-brightness characteristics (IUL characteristics), are determined. Table 1: Device results Device example Mixed Host / Dotand EQE at 1000 cd / m ² [%] Voltage at 1000 cd / m ² [V] CIE x / y 12 Example 3, 60% Host 1, 30% IrPPy 13.9 4.3 0.36 / 0.62 13 Example 4, 60% Host 1, 30% IrPPy 14.3 4.1 0.36 / 0.62 14 Example 6, 50% Host 1, 40% IrPPy 15.8 3.9 0.36 / 0.62 15 Example 8, 50% Host 1, 40% IrPPy 12.7 4.4 0.35 / 0.63 16 Example 6, 40% Host 1, 50% IrPIQ 8.7 5.0 0.68 / 0.31 17 Example 6, 60% Host 1, 30% IrF-CN-PPy 16.1 7.9 0:16 / 0.25 28 Example 23, 70% Host 1, 20% IrPPy 14.5 4.4 0.36 / 0.62 29 Example 24, 55% Host 1, 35% IrPPy 15.0 3.0 0.36 / 0.62 30 Example 25, 60% Host 1, 30% IrPPy 15.7 3.8 0.36 / 0.62 31 Example 26, 60% Host 1, 30% IrPPy 16.0 4.2 0.35 / 0.63 32 Example 27, 60% Host 1, 30% IrPPy 11.8 4.2 0.68 / 0.31

Furthermore, OLEDs are produced with the compound from Example 5 as hole injection material in the following layer structure: Hole injection layer (HIL) 40 nm Example 5 Hole transport layer (HTL) 5 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl) Emission layer (EML) 40 nm host: 4,4'-N, N'-dicarbazolylbiphenyl (CBP) dopant: 10% by volume doping, tris (1-phenylisoquinoline) iridium (IrPIQ) Electron conductor (ETL) 20 nm Alq; cathode 1 nm LiF, then 100 nm Al.

To characterize these OLEDs, the electroluminescence spectra, the external quantum efficiency (measured in%) as a function of the brightness, calculated from current-voltage-brightness characteristics (IUL characteristics), are determined. Table 2: Device results Device example EQE at 1000 cd / m ² [%] Voltage at 1000 cd / m ² [V] CIE x / y 17 13.0 3.8 0.68 / 0.31

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (15)

Compound according to formula (1),

where, for the symbols and indices used, X is identical or different at each occurrence and is C, Si, B, Al, N, P, P =O or P =S; Y is the same or different NAr ² , O or S at each occurrence; Ar ¹ at each occurrence, identically or differently together with the explicitly illustrated carbon atoms, is an aryl or heteroaryl group having 5 to 20 aromatic ring atoms which may be substituted by one or more radicals R; Ar ² is the same or different at each occurrence and is an aryl or heteroaryl group having 5 to 20 aromatic ring atoms which may be substituted by one or more R radicals; adjacent groups Ar ¹ and Ar ^{2 may} also be linked together by a single bond or by a group selected from CR ₂ , NR, BR, O or S; R is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (Ar ³ ) ₂ , N (R ² ) ₂ , C (= O) Ar ³ , C (= O) R ² , P (= O) (Ar ³ ) ₂ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted with one or more R ² radicals, wherein one or more non-adjacent CH ₂ groups is represented by R ² C = CR ² , C≡C, Si (R ² ) ₂ , C =O, C =S, C =NR ² , P (= O) (R ² ), SO, SO ₂ , NR ² , O, S or CONR ² replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each with one or more R ² radicals may be substituted, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R ² , or a combination of these systems, optionally two or more adjacent substituents R is a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more R ² radicals; R ¹ is the same or different at each occurrence, R or a group of formula (2),

wherein the symbols used have the same meaning as described for formula (1), the dashed bond indicates bonding to X and L is a single bond or a divalent group; two groups R ¹ , if n = 2, can also form a ring with each other; R ² is the same or different on each occurrence selected from the group consisting of H, D, F, Cl, Br, I, CN, NO ₂ , N (Ar ³ ) ₂ , N (R ³ ) ₂ , C (= O ) Ar ³ , C (O) R ³ , P (= O) (Ar ³ ) ₂ , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted with one or more R ³ radicals, wherein one or more non-adjacent CH ₂ groups is represented by R ³ C = CR ³ , C≡C, Si (R ³ ) ₂ , C =O, C =S, C =NR ³ , P (= O) (R ³ ), SO, SO ₂ , NR ³ , O, S or CONR ³ and wherein one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each with one or more radicals R ³ may be substituted, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ³ , or a combination of these systems, where optionally two or more adjacent substituents R ^{2 may form} a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system containing one or more radicals R ³ may be substituted; Ar ³ is the same or different at each occurrence, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which may be substituted with one or more non-aromatic radicals R ³ ; two Ar ² radicals which bind to the same N atom or P atom may also be bridged together by a single bond or a bridge selected from N (R ³ ), C (R ³ ) ₂ , O or S; R ³ in each occurrence is identically or differently selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or multiple H atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R ^{3 may form} together a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; n is 0 when X is B, Al, N, P = O or P = S, and is 1 when X is C or Si, and is 0 or 2 when X is P; the following compounds are excluded from the invention:

A compound according to claim 1, characterized in that X is the same or different Si, B, P, P = O or N at each occurrence and that Y is the same or different at each occurrence for NAr ² or O simultaneously. A compound according to claim 1 or 2, characterized in that all groups Y are chosen equal. Compound according to one or more of claims 1 to 3, characterized in that Ar ^{1 is the} same or different each occurrence of an aryl group having 6 to 10 aromatic carbon atoms which may be substituted by one or more R radicals, or a heteroaryl group of 5 to 13 aromatic ring atoms which may be substituted by one or more R radicals is Compound according to one or more of Claims 1 to 4, characterized in that the group Ar ^1, identical or different in each occurrence, represents a group of the following formula (3), (4), (5), (6) or (7) stands,

where # indicates the position of the linkage with Y, * indicates the position of the linkage with the nitrogen atom, and furthermore: W is the same or different CR or N at each occurrence; or two adjacent groups W stand for a group of the following formula (8) or (9),

wherein V is NR, O or S, Z is the same or different at each occurrence is CR or N and ^ indicate the corresponding adjacent groups W in the formula (3) to (7). A compound according to one or more of claims 1 to 5, selected from compounds of the formula (10),

wherein the symbols and indices used have the meanings mentioned in claim 1. A compound according to claim 6, selected from the compounds of formula (10a),

wherein the symbols and indices used have the meanings mentioned in claim 1. Compound according to one or more of claims 1 to 7, characterized in that Ar ^{2 is the} same or different at each occurrence for an aryl group having 6 to 10 aromatic carbon atoms which may be substituted by one or more R radicals, or a heteroaryl group having 5 to 13 aromatic ring atoms which may be substituted by one or more R radicals is. A compound according to one or more of claims 1 to 8, selected from the compounds of the formulas (11) or (12):

wherein the symbols and indices used have the meanings given in claim 1 and E is the same or different at each occurrence as a single bond, CR ₂ , NR, BR, O or S. A compound according to claim 9, selected from the compounds of the formulas (11a) or (12a),

wherein the symbols and indices used have the meanings given in claims 1 and 9. Process for the preparation of a compound according to one or more of claims 1 to 10, comprising the reaction steps: a) Preparation of a triamine, a diamino alcohol or an aminodialcohol; b) triple deprotonation of the triamine, diamino alcohol or aminodialcohol with a base; and c) Reaction of the deprotonated triamine, the deprotonated diaminoalcohol or the deprotonated aminodialcohol with an electrophile carrying three leaving groups. An oligomer, polymer or dendrimer comprising one or more compounds according to one or more of claims 1 to 10, wherein one or more bonds of the compound according to the invention to the polymer, oligomer or dendrimer are present. Use of a compound according to one or more of claims 1 to 10 or 12 in an electronic device, in particular in an organic electroluminescent device. Electronic device comprising at least one compound according to one or more of claims 1 to 10 or 12, in particular selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light emitting electrochemical cells, organic laser diodes, and organic plasmon emitting devices. Electronic device according to claim 14, which is an organic electroluminescent device, characterized in that the compound according to one or more of claims 1 to 10 or 12 as matrix material for fluorescent or phosphorescent emitters and / or in a hole blocking layer and / or in an electron transport layer and / or or in an electron-blocking or exciton-blocking layer and / or in a hole transport layer.