CN103804346A - Thioxanthone oxide derivative, and preparation method and application thereof - Google Patents

Thioxanthone oxide derivative, and preparation method and application thereof Download PDF

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CN103804346A
CN103804346A CN201210444090.4A CN201210444090A CN103804346A CN 103804346 A CN103804346 A CN 103804346A CN 201210444090 A CN201210444090 A CN 201210444090A CN 103804346 A CN103804346 A CN 103804346A
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base
phenanthrene
coughed
beautiful jade
amido
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CN103804346B (en
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汪鹏飞
王会
刘卫敏
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses a kind of oxidation thioxanthone analog derivative, its structural formula is as follows: In formula (1) and formula (2), R1, R2, R3, R4, R5, R6, R7, R8 are respectively selected from one of hydrogen atom, alkoxy, alkylthio group, alkylamino radical, aryl amine, aryloxy group, arylthio, aryl, heteroaromatic group, and at least one in R1, R2, R3, R4, R5, R6, R7, R8 is aromatic group. The invention also discloses the preparation method and application of the oxidation thioxanthone analog derivative, which can be used as the organic luminous layer of organic electroluminescence device.

Description

Oxidation thioxanthone analog derivative, preparation method and application thereof
Technical field
The present invention relates to be oxidized thioxanthone analog derivative and preparation method thereof, and the application of described oxidation thioxanthone analog derivative in organic electroluminescence device.
Background technology
From 1987, the people such as the C.W.Tang of Kodak utilize first vacuum to steam and cross legal system for the device (C.W.Tang of small molecules film sandwich style, S.A.Vanslyke, Applied PhysicsLetters, 1987,51,913), brand-new epoch have just been stepped in the research of electroluminescent organic material.Organic electroluminescence device is mainly made up of positive electrode, negative potential, active coating.Wherein, active coating is luminescent layer, is clipped between positive and negative electrode layer, forms the sandwich structure of similar sandwich.In order to improve the injection of current carrier and transmission, improve the working efficiency of device, conventionally also to introduce current carrier (hole and electronics) input horizon, carrier blocking layers and exciton barrier-layer.Hole and electronics are injected into organic layer from positive and negative electrode respectively under the effect of extra electric field, and in luminescent layer, meet, compound, radioluminescence.
In recent years, the organic electroluminescence device of high-level efficiency, low driving voltage, high stability, different emission had been seen in report (Xiao, L.X. in succession; Kido, J.J., Adv.Mater.2011,23 (8), 926; Chaskar, A.; Wong, K.-T., Adv.Mater.2011,23 (34), 3876).Organic electroluminescence device, particularly organic electro phosphorescent device, received general concern.Be mainly because the phosphorescent light-emitting materials of such device can effectively utilize the triplet exciton of hole and electron recombination formation, make the theoretical internal quantum of such device reach 100%, be 4 times of fluorescence electroluminescent device.But, phosphorescence device truly, particularly blue phosphorescent device or few, its basic reason is there is no suitable luminescent layer material of main part.
Suitable luminescent layer material of main part must meet following requirement: have the triplet energy state higher than phosphorescent light-emitting materials, suppress the energy passback of energy from object dye molecule to host molecule; There is the carrier transmission performance of balance; The film-forming properties having possessed and chemical stability, to improve the work-ing life of device.Because material of main part will possess the triplet energy state higher than phosphorescent light-emitting materials, this just requires the band gap of material of main part must quite widely produce high triplet energy state.And broad-band gap means that material must possess short conjugated electrons system, and injection and the transmission of short conjugated system to current carrier is disadvantageous beyond doubt.How at wide energy gap to guarantee finding trim point between high triplet energy level and good carrier transport, be the bottleneck of phosphorescent light body material development.
Summary of the invention
First technical problem that the present invention will solve is to provide oxidation thioxanthone analog derivative.
Second technical problem that the present invention will solve is to provide the preparation method of oxidation thioxanthone analog derivative.
The 3rd technical problem that the present invention will solve is to provide the application of oxidation thioxanthone analog derivative.
The invention provides oxidation thioxanthone analog derivative, its structural formula is as follows:
Figure BDA00002372523900021
In formula (1) and formula (2), R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be selected from respectively the one in hydrogen atom, alkoxyl group, alkylthio, alkylamino radical, aryl amine, aryloxy, arylthio, aryl, heteroaromatic group, and R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8in have one at least for aromatic group;
Further,
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8alkoxyl group be the alkoxyl group of 1 to 20 carbon atom;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8alkylthio be the alkylthio of 1 to 20 carbon atom;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8alkylamino radical be not substituted alkyl amido or the substituted alkyl amido of 1 to 20 carbon atom;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8aryl amine be the aryl amine of 6 to 30 carbon atoms;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8aryloxy be phenoxy group;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8arylthio be thiophenyl;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8aryl be aryl or the substituted aryl of 6 to 30 carbon atoms;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8hetero-aromatic ring be the fragrant heterocycle of 5 to 50 annular atomses or the fragrant heterocycle of replacement.
Further,
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkoxyl group of 1 to 20 carbon atom be: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy, neopentyl oxygen, tertiary pentyloxy, hexyloxy, 2-methyl pentyloxy;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkylthio of 1 to 20 carbon atom be: methylthio group, ethylmercapto group, rosickyite base, positive butylthio, secondary butylthio, tertiary butylthio;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkylamino radical of 1 to 20 carbon atom be: methylamino, ethylamino-, Propylamino, butylamine base, amylamine base, isoamyl amido, neopentyl amine base, tertiary amylamine base, hexylamine base, dimethylin, diethylin, dipropyl amido, dibutyl amino, diamyl amido, diisoamyl amido, two neopentyl amine bases, two tertiary amylamine bases, dihexylamine base;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the aryl amine of 6 to 30 carbon atoms be: o-, m-, p-aminomethyl phenyl amido, o-, m-, p-ethylphenyl amido, o-, m-, p-propyl group phenyl amido, o-, m-, p-isopropyl phenyl amido, o-, m-, p-p-methoxy-phenyl amido, o-, m-, p-ethoxyl phenenyl amido, o-, m-, p-propoxy-phenyl amido, o-, m-, p-difluorophenyl amido, o-, m-, p-chlorophenyl amido, o-, m-, p-bromo phenyl amido, o-, m-, p-iodine substituted phenyl amido, two (o-, m-, p-aminomethyl phenyl) amido, two (o-, m-, p-ethylphenyl) amido, two (o-, m-, p-propyl group phenyl) amido, two (o-, m-, p-isopropyl phenyl) amido, two (o-, m-, p-p-methoxy-phenyl) amido, two (o-, m-, p-ethoxyl phenenyl) amido, two (o-, m-, p-propoxy-phenyl) amido, two (o-, m-, p-difluorophenyl) amido, two (o-, m-, p-chlorophenyl) amido, two (o-, m-, p-bromo phenyl) amido, two (o-, m-, p-iodine substituted phenyl) amido,
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the aryl of 6 to 30 carbon atoms be: phenyl, phenylbenzene, triphenyl, naphthacenyl, pyrenyl, fluorenes, spiral shell fluorenes;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the substituted aryl of 6 to 30 carbon atoms be: o-, m-, p-tolyl, xylyl, o-, m-, p-cumyl, trimethylphenyl, 9,9 '-dimethyl fluorenyl, 9,9 '-spiral shell, two fluorenyls;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the fragrant heterocycle of 5 to 50 annular atomses be: 1-pyrryl, 2-pyrryl, 3-pyrryl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indyl, 2-indyl, 3-indyl, 4-indyl, 5-indyl, 6-indyl, 7-indyl, 1-pseudoindoyl, 2-pseudoindoyl, 3-pseudoindoyl, 4-pseudoindoyl, 5-pseudoindoyl, 6-pseudoindoyl, 7-pseudoindoyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl, diphenylene-oxide-2-base, 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base, 7-isobenzofuran-base, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 1-carbazyl, 2-carbazyl, 3-carbazyl, 4-carbazyl, 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, 1-acridyl, 2-acridyl, 3-acridyl, 4-acridyl, 9-acridyl, 1,7-phenanthrene is coughed up beautiful jade-2-base, 1,7-phenanthrene is coughed up beautiful jade-3-base, 1,7-phenanthrene is coughed up beautiful jade-4-base, 1,7-phenanthrene is coughed up beautiful jade-5-base, 1,7-phenanthrene is coughed up beautiful jade-6-base, 1,7-phenanthrene is coughed up beautiful jade-8-base, 1,7-phenanthrene is coughed up beautiful jade-9-base, 1,7-phenanthrene is coughed up beautiful jade-10-base, 1,8-phenanthrene is coughed up beautiful jade-2-base, 1,8-phenanthrene is coughed up beautiful jade-3-base, 1,8-phenanthrene is coughed up beautiful jade-4-base, 1,8-phenanthrene is coughed up beautiful jade-5-base, 1,8-phenanthrene is coughed up beautiful jade-6-base, 1,8-phenanthrene is coughed up beautiful jade-7-base, 1,8-phenanthrene is coughed up beautiful jade-9-base, 1,8-phenanthrene is coughed up beautiful jade-10-base, 1,9-phenanthrene is coughed up beautiful jade-2-base, 1,9-phenanthrene is coughed up beautiful jade-3-base, 1,9-phenanthrene is coughed up beautiful jade-4-base, 1,9-phenanthrene is coughed up beautiful jade-5-base, 1,9-phenanthrene is coughed up beautiful jade-6-base, 1,9-phenanthrene is coughed up beautiful jade-7-base, 1,9-phenanthrene is coughed up beautiful jade-8-base, 1,9-phenanthrene is coughed up beautiful jade-10-base, 1,10-phenanthrene is coughed up beautiful jade-2-base, 1,10-phenanthrene is coughed up beautiful jade-3-base, 1,10-phenanthrene is coughed up beautiful jade-4-base, 1,10-phenanthrene is coughed up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2,9-phenanthrolines-3-base, 2,9-phenanthrolines-4-base, 2,9-phenanthrolines-5-base, 2,9-phenanthrolines-6-base, 2,9-phenanthrolines-7-base, 2,9-phenanthrolines-8-base, 2,9-phenanthrolines-10-base, 2,8-phenanthrene is coughed up beautiful jade-1-base, 2,8-phenanthrene is coughed up beautiful jade-3-base, 2,8-phenanthrene is coughed up beautiful jade-4-base, 2,8-phenanthrene is coughed up beautiful jade-5-base, 2,8-phenanthrene is coughed up beautiful jade-6-base, 2,8-phenanthrene is coughed up beautiful jade-7-base, 2,8-phenanthrene is coughed up beautiful jade-9-base, 2,8-phenanthrene is coughed up beautiful jade-10-base, 2,7-phenanthrene is coughed up beautiful jade-1-base, 2,7-phenanthrene is coughed up beautiful jade-3-base, 2,7-phenanthrene is coughed up beautiful jade-4-base, 2,7-phenanthrene is coughed up beautiful jade-5-base, 2,7-phenanthrene is coughed up beautiful jade-6-base, 2,7-phenanthrene is coughed up beautiful jade-8-base, 2,7-phenanthrene is coughed up beautiful jade-9-base, 2,7-phenanthrene is coughed up beautiful jade-10-base, 1-phenazinyl, 2-phenazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, lysivane base, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazan base, 2-thienyl, 3-thienyl, dibenzothiophene-2-base, 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tertiary butyl pyrroles-4-base, 3-(2-phenyl propyl) pyrroles one-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tertiary butyl-1-indyl, the 4-tertiary butyl-1-indyl, the 2-tertiary butyl-3-indyl, the 4-tertiary butyl-3-indyl.
The preparation method who the invention provides oxidation thioxanthone analog derivative, comprises the following steps:
A, by thioxanthone compounds and concentration, higher than the nitrate solution of 10M, the ratio take mol ratio as 1:0.1 ~ 100 is not dissolved in acetonitrile, stirs, and adds water precipitation, filters, and filtrate recrystallization, obtains the oxidation thioxanthone analog derivative shown in formula (1);
The consumption of acetonitrile is very little on the impact of this reaction system, does not need special restriction, considers from Applied economy angle, and it is few as much as possible that consumption should be.When stirring, can regulate as required stir speed (S.S.), churning time etc., should be appreciated that, these factors do not affect the formation of final oxidation thioxanthone analog derivative.The add-on of water regulates according to practical situation.After adding water, produce the crude product containing the oxidation thioxanthone compound shown in formula (1), this reaction is the oxidizing reaction that nitrate is made oxygenant.Above-mentioned reaction at room temperature.
Or
B, by thioxanthone compounds and hydrogen peroxide solution, the ratio take mol ratio as 1:0.1 ~ 100 is dissolved in acetic acid, refluxes, and the cooling precipitation of separating out, filters, and filtrate recrystallization, obtains being oxidized thioxanthone analog derivative shown in formula (2);
General 30% the hydrogen peroxide solution that adopts.The consumption of acetic acid is very little on the impact of this reaction system, does not need special restriction, considers from Applied economy angle, and it is few as much as possible that consumption should be.The cooling precipitation of separating out is that this reaction is the oxidizing reaction that nitrate is made oxygenant containing the crude product of the oxidation thioxanthone compound shown in formula (2).
Described formula (1) and formula (2) are as follows:
In formula, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be selected from respectively the one in hydrogen atom, alkoxyl group, alkylthio, alkylamino radical, aryl amine, aryloxy, arylthio, aryl, heteroaromatic group, and R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8in have one at least for aromatic group.
Further, the structural formula of described thioxanthone compounds is:
Figure BDA00002372523900052
In formula (5), R 1, R 2, R 3, R4, R 5, R 6, R 7, R 8definition with the definition in " oxidation thioxanthone analog derivative " above, be selected from respectively the one in hydrogen atom, alkoxyl group, alkylthio, alkylamino radical, aryl amine, aryloxy, arylthio, aryl, heteroaromatic group, and R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8in have one at least for aromatic group;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8further definition with the definition in " oxidation thioxanthone analog derivative " above.
Described nitrate solution is the solution such as SODIUMNITRATE, ammonium nitrate, iron nitrate or nitrous acid iron.
The solvent that described recrystallization is selected is one or more mixed solvents in the organic solvents such as methyl alcohol, ethanol, methylene dichloride, methyl-sulphoxide, diformamide.
Described backflow is to reflux 2～12 hours under 25～100 ℃ of conditions.
The invention provides the application of oxidation thioxanthone analog derivative, this oxidation thioxanthone analog derivative can be used as the organic luminous layer of organic electroluminescence device.
Generally, this oxidation thioxanthone analog derivative is the main body luminescent material as organic luminous layer, can add other dyestuff as object luminescent material.
Organic electroluminescence device comprises negative electrode, anode and organic thin film layer, and organic thin film layer is between negative electrode and anode; Described organic thin film layer comprises organic luminous layer, and described oxidation thioxanthone analog derivative is the material of main part as organic luminous layer.This organic electroluminescence device can be used in organic integrated circuits, organic solar batteries, organic laser or organic sensor.
Preferably, this oxidation thioxanthone analog derivative can be made electrophosphorescence device by Doping Phosphorus photoinitiator dye.Described phosphorescent coloring can be selected from the complex compound of the metals such as Ir (iridium), Pt (platinum), Os (osmium), Ru (ruthenium).Preferably, the complex compound that described phosphorescent coloring is Ir.As, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls of blue light-emitting close iridium (being called for short FIrpic), and three (2-phenylpyridine) iridium of green light (is called for short Ir (ppy) 3), three [1-phenyl isoquinolin quinoline-C2, the N] iridium (III) glowing (is called for short Ir (piq) 3).
Preferably, the doping content of phosphorescent coloring is 5 ~ 15wt%.
Described organic thin film layer also comprises hole injection layer, hole transmission layer and electron transfer layer etc.
Preferably, the structure of organic electroluminescence device is: substrate/anode/hole transmission layer/organic luminous layer/electron transfer layer/negative electrode.
Substrate is transparent, can be glass or flexible substrate.Described flexible substrate can be a kind of material in polyester, poly-phthalimide compounds.
Anode layer can be inorganic materials or organic conductive polymkeric substance.Described inorganic materials is generally the metal oxides such as tin indium oxide (ITO), zinc oxide, zinc tin oxide, or the higher metal of work function such as gold and silver, copper; Most preferably be ITO.Described organic conductive polymkeric substance is preferably a kind of material in Polythiophene/polyvinylbenzenesulfonic acid sodium (PEDOT:PSS), polyaniline (PANI).
Cathode layer generally adopts the lower metals of work function such as lithium, magnesium, calcium, strontium, aluminium or indium, or a kind of and copper, gold or silver-colored alloy in them, or the electrode layer that alternately forms of above-mentioned metal or alloy and metal fluoride.Be preferably LiF layer and Mg:Ag alloy layer successively.
Hole transmission layer generally adopts tri-arylamine group material.Be preferably N, N '-bis--(1-naphthyl)-N, N '-phenylbenzene-1,1-xenyl-4,4-diamines (NPB).
Electron transfer layer generally adopts nitrogen heterocycles material.Be preferably 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
Organic luminous layer is the oxidation thia anthracyclinone derivatives shown in formula (1) or (2).Preferably, the oxidation thia anthracyclinone derivatives that described organic luminous layer represents using formula (1) or (2) is as material of main part, with FIrpic, Ir (ppy) 3or Ir (piq) 3as object luminescent material.
The process that is prepared with organic electroluminescence devices take oxidation thia anthracyclinone derivatives of the present invention as material of main part as:
1. use successively commercial clean-out system (preferentially selecting Decon 90 clean-out systems), deionized water and organic solution (preferentially to select methyl alcohol, ethanol, a kind of or two kinds and above mixed solvent in acetone, acetonitrile, tetrahydrofuran (THF)) divide several steps to clean the glass substrate with anode;
2. by the method for vacuum-evaporation, the hole transmission layer of evaporation device;
3. the luminescent layer of evaporation device;
4. the electron transfer layer of evaporation device;
5. prepare metallic cathode by the method for evaporation or sputter again.
For example, the preparation process of OLED is:
Sheet glass supersound process in commercial clean-out system of ITO transparency conducting layer will be coated with, in deionized water, rinse, ultrasonic oil removing in the mixed solvent of acetone and ethanol, under clean environment, be baked to and remove moisture content completely, irradiate 1 ~ 100 minute with UV-light cleaning machine, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10 -5～9 × 10 -3pa, first evaporation CuPc 1 ~ 15nm on above-mentioned anode tunic, continues evaporation NPB as hole transmission layer, and evaporation rate-controlling is 50 ~ 75nm at 0.1 ~ 0.5nm/s. evaporation thickness;
On hole transmission layer, continue evaporation one deck luminescent layer, luminescent layer forms with the oxidation thia anthracyclinone derivatives doping shown in phosphorescent light-emitting materials and formula of the present invention (1) or (2), the evaporation speed ratio of oxidation thia anthracyclinone derivatives and phosphorescent light-emitting materials is 100:1, the doping content that phosphorescent light-emitting materials is oxidized in thia anthracyclinone derivatives is in the present invention x, x is 5 ~ 15wt%, and the total speed of its evaporation is 0.1nm/s, and evaporation total film thickness is 30nm;
Continue the electron transfer layer of evaporation one deck TPBI as device, its evaporation speed is 0.lnm/s again, and evaporation total film thickness is 35nm;
Finally, on above-mentioned electron transfer layer, evaporation LiF layer and Mg:Ag alloy layer are as the cathode layer of device successively, and wherein the thickness of LiF layer is 0.5nm, and the evaporation speed of Mg:Ag alloy layer is 2.0～3.0nm/s, and thickness is 100nm.
The invention has the advantages that:
1, oxidation thioxanthone analog derivative of the present invention can be used as the luminescent layer material in organic electroluminescence device.Its oxidation thioxanthone molecule, owing to introducing multiple electron deficiency groups, has certain electron transport ability.Thioxanthone compound is a kind of conventional photosensitizer, and it has high triplet energies and little singlet state triplet state energy gap; Thioxanthone after oxidation has continued to keep high triplet energy level, and by the modification of different substituents, can do to change to highest occupied molecular orbital (HOMO) energy level and minimum track (LUMO) energy level that do not occupy that are oxidized rear thioxanthone molecule, the energy barrier of reduction and adjacent layers material, the injection of the current carrier of being more convenient for and transmission; In addition, because being oxidized, the present invention in thioxanthone analog derivative, introduces large substituting group, improved its film-forming properties and chemical stability, be conducive to prepare the device that stability is higher, the organic electroluminescence device that utilizes derivative of the present invention to prepare has high device efficiency and low cut-in voltage.
2, the present invention adopts easy method to synthesize a series of oxidation thioxanthone analog derivatives with high electric transmission speed.
3, utilize oxidation thioxanthone analog derivative of the present invention to there is high brightness, high efficiency high-performance as the material of main part organic electroluminescence device prepared by various phosphorescent colorings that adulterates.Experiment is found, by selecting suitable phosphorescent coloring, can realize the high efficiency light-emittings such as redness, green, blueness.
Accompanying drawing explanation
Fig. 1 is abosrption spectrogram (a), fluorescence spectrum figure (b), the 77K phosphorescence spectrum figure (c) of the oxidation thioxanthone analog derivative of the embodiment of the present invention 4.
Fig. 2 is abosrption spectrogram (a), fluorescence spectrum figure (b), the 77K phosphorescence spectrum figure (c) of the oxidation thioxanthone analog derivative of the embodiment of the present invention 14.
Fig. 3 is the structural representation that the present invention is oxidized the organic electroluminescent light device that thioxanthone analog derivative makes as material of main part.
Fig. 4 be oxidation thioxanthone analog derivative based on the embodiment of the present invention 4 containing 7wt%Ir (ppy) 3eL (a) under different brightness, L-V graphic representation (b).
Embodiment
In order to understand better the content of patent of the present invention, will further illustrate technical scheme of the present invention by specific embodiment below.
Herein, thioxanthone compounds all can prepare by prior art.For example, the thioxanthone compounds of embodiment 1 ~ 20 can be with reference to WO 2012/063751 A1; J.Chem.Soc.Perkin trans.11991; J.Org.Chem., Vol.67, No.22,2002; WO 2012/008558 A1; WO 2006/114966A1 makes, and the thioxanthone compounds of embodiment 21 ~ 28 can be with reference to Contribution From TheChemical Laboratory OfIowa State College, vol.24,1914 ~ 1916; WO 2012/060234A1.
Fig. 3 is the structural representation that the present invention is oxidized the organic electroluminescent light device that thioxanthone analog derivative makes as material of main part.
Embodiment 1
Synthetic oxidation thioxanthone analog derivative Comp-1
Figure BDA00002372523900081
By the nitrate solution of 2,7-phenylbenzene thioxanthone and 1M, the ratio take mol ratio as 1:4 is dissolved in acetonitrile, and stirring at room temperature 4 hours, adds a large amount of water precipitations, after filtration, must be oxidized thioxanthone analog derivative Comp-1 with ethyl alcohol recrystallization, and productive rate is about 70%; M/z:380.09 (100.0%), 381.09 (28.0%), 382.08 (4.6%), 381.08(4.2%), 382.09(1.7%).M/z is the mass-to-charge ratio of target molecule in Low Resolution Mass Spectra.
Embodiment 2
Synthetic oxidation thioxanthone analog derivative Comp-2:
Figure BDA00002372523900082
With embodiment 1, with 2,7-bis-(2 '-xenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-2, productive rate is about 70%; M/z:532.15 (100.0%), 533.15 (40.8%), 534.16 (8.0%), 533.14 (4.8%).
Embodiment 3
Synthetic oxidation thioxanthone analog derivative Comp-3:
Figure BDA00002372523900091
With embodiment 1, with 2,7-bis-(3 ', 5 '-terphenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-3, productive rate is about 70%.m/z:684.21(100.0%),685.22(53.3%),686.23(14.6%),685.21（3.2%），686.22（1.9%）。
Embodiment 4
Synthetic oxidation thioxanthone analog derivative Comp-4:
Figure BDA00002372523900092
With embodiment 1, with 2,7-bis-(9 ', 9 '-dimethyl fluorenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-4, productive rate is about 70%; M/z:612.21 (100.0%), 613.22 (47.1%), 614.22 (11.6%), 613.21(5.2%), 614.23(2.9%).
Fig. 1 is the optical physics data (abosrption spectrogram (a), fluorescence spectrum figure (b), 77K phosphorescence spectrum figure (c)) of the prepared Comp-4 of the present invention, due to the n-π * transition that in absorption spectrum, the Weak Absorption band at 325nm place is carbonyl; Fluorescence and phosphorescence spectrogram shows that this molecule is very strong without fluorescence and phosphorescence intensity.Can estimate energy gap and the triplet energy state of Comp-4 according to optical physics data, to assess its performance and application.
Fig. 4 be oxidation thioxanthone analog derivative based on the embodiment of the present invention 4 containing 7wt%Ir (ppy) 3eL (a) under different brightness, L-V graphic representation (b).Be that Comp-4 is green phosphorescent device result prepared by material of main part, device cut-in voltage is 3.9V, and high-high brightness is 4132cd/m 2.Find out the increase along with brightness from Fig. 4 a, the luminous of Comp-4 self strengthens gradually.
Embodiment 5
Synthetic oxidation thioxanthone analog derivative Comp-5:
Figure BDA00002372523900101
With embodiment 1, with 2,7-bis-(9 ', 9 '-spiral shell, two fluorenes) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-5, productive rate is about 70%; M/z:872.27 (100.0%), 873.28 (69.8%), 874.28 (24.9%), 873.27(5.2%).
Embodiment 6
Synthetic oxidation thioxanthone analog derivative Comp-6:
Figure BDA00002372523900102
With embodiment 1, with 2,7-bis-(9 ', 10 '-phenyl phenanthryl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-6, productive rate is about 70%; M/z:712.24 (100.0%), 713.25 (55.8%), 714.25 (16.0%), 713.27(2.3%).
Embodiment 7
Synthetic oxidation thioxanthone analog derivative Comp-7:
With embodiment 1, with 3,6-bis-(2 ', 4 ', 6 '-trimethylphenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-7, productive rate is about 70%; M/z:464.18 (100.0%), 465.17 (34.3%), 466.17 (6.0%), 466.19(5.3%), 465.18(2.5%).
Embodiment 8
Synthetic oxidation thioxanthone analog derivative Comp-8:
With embodiment 1, with 2,7-bis-(3 '-quinolyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-8, productive rate is about 70%; M/z:482.11 (100.0%), 483.11 (35.1%), 484.12 (5.5%), 483.12(1.3%).
Embodiment 9
Synthetic oxidation thioxanthone analog derivative Comp-9:
Figure BDA00002372523900112
With embodiment 1, with 2,7-bis-(2 '-benzothiazolyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-9, productive rate is about 70%; M/z:592.06 (100.0%), 593.07 (40.2%), 594.06 (13.5%), 593.06(3.5%) 594.06 (1.3%).
Embodiment 10
Synthetic oxidation thioxanthone analog derivative Comp-10:
With embodiment 1, with 2,7-bis-(2 '-cumarone) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, must be oxidized thioxanthone analog derivative Comp-10, productive rate is about 70%; M/z:560.11 (100.0%), 561.11 (41.1%), 562.12 (8.5%), 563.12(1.3%).
Embodiment 11
Synthetic oxidation thioxanthone analog derivative Comp-11:
Figure BDA00002372523900121
By the hydrogen peroxide of 2,7-phenylbenzene thioxanthone and 30%, the ratio take mol ratio as 1:1 is dissolved in acetic acid, and in 100 ℃ of backflows, the cooling precipitation of separating out, filters and use ethyl alcohol recrystallization, obtains being oxidized thioxanthone analog derivative Comp-11, and productive rate is about 90%; M/z:396.08 (100.0%), 397.09 (27.3%), 398.08 (4.6%), 397.08(1.3%).
Embodiment 12
Synthetic oxidation thioxanthone analog derivative Comp-12:
Figure BDA00002372523900122
With embodiment 11, with 3,6-bis-(2 '-xenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-12, productive rate is about 90%; M/z:548.14 (100.0%), 549.14 (40.4%), 550.15 (8.9%), 549.13 (4.4%), 550.14 (0.9%).
Embodiment 13
Synthetic oxidation thioxanthone analog derivative Comp-13:
With embodiment 11, with 2,7-bis-(3 ', 5 '-terphenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-13, productive rate is about 90%; M/z:700.21 (100.0%), 701.21 (54.3%), 702.21 (14.9%), 701.23 (5.0%).
Embodiment 14
Synthetic oxidation thioxanthone analog derivative Comp-14:
Figure BDA00002372523900131
With embodiment 11, with 2,7-bis-(9 ', 9 '-dimethyl fluorenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-14, productive rate is about 90%; M/z:628.21 (100.0%), 629.21 (47.8%), 630.21 (11.6%), 629.20 (4.7%), 630.22 (1.1%).
Fig. 2 is the optical physics data (abosrption spectrogram (a), fluorescence spectrum figure (b), 77K phosphorescence spectrum figure (c)) of the prepared Comp-14 of the present invention, due to the n-π * transition that in absorption spectrum, the Weak Absorption band at 330nm place is carbonyl; Fluorescence and phosphorescence spectrogram shows that this molecule is very strong without fluorescence and phosphorescence intensity.Can estimate energy gap and the triplet energy state of Comp-14 according to optical physics data, to assess its performance and application.
Embodiment 15
Synthetic oxidation thioxanthone analog derivative Comp-15:
Figure BDA00002372523900132
With embodiment 11, with 2,7-bis-(9 ', 9 '-spiral shell, two fluorenes) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-15, productive rate is about 90%; M/z:888.27 (100.0%), 889 .27 (70.1%), 890.28 (24.1%), 889.28 (2.7%).
Embodiment 16
Synthetic oxidation thioxanthone analog derivative Comp-16:
Figure BDA00002372523900133
With embodiment 11, with 2,7-bis-(9 ', 10 '-phenyl phenanthryl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-16, productive rate is about 90%; M/z:728.24 (100.0%), 729.24 (70.1%), 730.25 (24.1%), 729.23 (2.7%), 730.25 (1.2%).
Embodiment 17
Synthetic oxidation thioxanthone analog derivative Comp-17:
Figure BDA00002372523900141
With embodiment 11, with 3,6-bis-(2 ', 4 ', 6 '-trimethylphenyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-17, productive rate is about 90%; M/z:480.18 (100.0%), 481.18 (34.8%), 482.19 (6.4%), 482.18 (1.5%).
Embodiment 18
Synthetic oxidation thioxanthone analog derivative Comp-18:
With embodiment 11, with 2,7-bis-(3 '-quinolyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-18, productive rate is about 90%; M/z:498.10 (100.0%), 499.10 (33.9%), 500.11 (6.4%), 499.11 (3.5%), 500.12 (1.3%).
Embodiment 19
Synthetic oxidation thioxanthone analog derivative Comp-19:
Figure BDA00002372523900143
With embodiment 11, with 2,7-bis-(2 '-benzothiazolyl) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-19, productive rate is about 90%; M/z:608.06 (100.0%), 609.06 (42.8%), 610.05 (13.7%), 609.05 (4.7%), 610.04.12 (1.7%).
Embodiment 20
Synthetic oxidation thioxanthone analog derivative Comp-20:
Figure BDA00002372523900151
With embodiment 11, with 2,7-bis-(2 '-cumarone) thioxanthone replacement, 2,7-phenylbenzene thioxanthone, obtain being oxidized thioxanthone analog derivative Comp-20, productive rate is about 90%; M/z:576.10 (100.0%), 577.11 (40.4%), 578.11 (9.3%), 577.10(2.0%).
Embodiment 21
Synthetic oxidation thioxanthone analog derivative Comp-21
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-thiophenyl-thioxanthone; J.Am.Chem.Soc.1947, p.1229-123; J.Am.Chem.Soc.1997, vol.93, p.1517-1522).
By the nitrate solution of 2-hexylamine base-7-thiophenyl-thioxanthone and 1M, ratio take mol ratio as 1:4 is dissolved in acetonitrile, and stirring at room temperature 4 hours, adds a large amount of water precipitations, after filtration, must be oxidized thioxanthone analog derivative Comp-21 with ethyl alcohol recrystallization, productive rate is about 70%.m/z：435.13(100.0%)，436.14(27.2%)，437.13(9.4%)，437.14（3.9%）。
Embodiment 22
Synthetic oxidation thioxanthone analog derivative Comp-22
Figure BDA00002372523900153
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-phenoxy group-thioxanthone; J.Am.Chem.Soc.1947, p.1229-123; J.Med.Chem, 1982, vol.25, p.220-227).
By the nitrate solution of 2-hexylamine base-7-phenoxy group-thioxanthone and 1M, ratio take mol ratio as 1:4 is dissolved in acetonitrile, and stirring at room temperature 4 hours, adds a large amount of water precipitations, after filtration, must be oxidized thioxanthone analog derivative Comp-22 with ethyl alcohol recrystallization, productive rate is about 70%.m/z：419.16(100.0%)，420.15(27.4%)，421.16(4.4%)，421.15（1.4%）。
Embodiment 23
Synthetic oxidation thioxanthone analog derivative Comp-23
Figure BDA00002372523900161
The synthesized reference document of 2-hexyloxy-7-m-ethyl aniline base-thioxanthone (J.Am.Chem.Soc.1997, vol.93, p.1517-1522; WO 2006/114966 A1).
By the nitrate solution of 2-hexyloxy-7-m-ethyl aniline base-thioxanthone and 1M, ratio take mol ratio as 1:4 is dissolved in acetonitrile, and stirring at room temperature 4 hours, adds a large amount of water precipitations, after filtration, must be oxidized thioxanthone analog derivative Comp-23 with ethyl alcohol recrystallization, productive rate is about 70%.m/z：447.19(100.0%)，448.19(30.5%)，449.19(5.1%)，449.18（2.3%）。
Embodiment 24
Synthetic oxidation thioxanthone analog derivative Comp-24
Figure BDA00002372523900162
Synthesized reference document (Patent:GB932494,1958 of the own sulfydryl-7-of 2-cumic aldehyde amido-thioxanthone; Chem.Abstr.1964, vol.61,9477; WO 2006/114966 A1).
By the nitrate solution of 2-hexyloxy-7-cumic aldehyde amido-thioxanthone and 1M, ratio take mol ratio as 1:4 is dissolved in acetonitrile, and stirring at room temperature 4 hours, adds a large amount of water precipitations, after filtration, must be oxidized thioxanthone analog derivative Comp-24 with ethyl alcohol recrystallization, productive rate is about 70%.m/z：477.18(100.0%)，478.19(32.3%)，479.19(10.3%)，449.18（1.5%）。
Embodiment 25
Synthetic oxidation thioxanthone analog derivative Comp-25
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-thiophenyl-thioxanthone; J.Am.Chem.Soc.1947, p.1229-123; J.Am.Chem.Soc.1997, vol.93, p.1517-1522).
By the hydrogen peroxide of 2-hexylamine base-7-thiophenyl-thioxanthone and 30%, be dissolved in acetic acid take mol ratio as the ratio of 1: 1, in 100 ℃ of backflows, the cooling precipitation of separating out, filter and use ethyl alcohol recrystallization, must be oxidized thioxanthone analog derivative Comp-25, productive rate is about 90%.m/z：451.13(100.0%)，452.14(29.1%)，453.14(9.0%)，453.13（2.3%）。
Embodiment 26
Synthetic oxidation thioxanthone analog derivative Comp-26
Figure BDA00002372523900171
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-phenoxy group-thioxanthone; J.Am.Chem.Soc.1947, p.1229-123; J.Med.Chem, 1982, vol.25, p.220-227).
By the hydrogen peroxide of 2-hexylamine base-7-phenoxy group-thioxanthone and 30%, be dissolved in acetic acid take mol ratio as the ratio of 1: 1, in 100 ℃ of backflows, the cooling precipitation of separating out, filter and use ethyl alcohol recrystallization, must be oxidized thioxanthone analog derivative Comp-26, productive rate is about 90%.m/z：435.15(100.0%)，436.15(28.4%)，437.16(5.8%)，437.15（1.7%）。
Embodiment 27
Synthetic oxidation thioxanthone analog derivative Comp-27
The synthesized reference document of 2-hexyloxy-7-m-ethyl aniline base-thioxanthone (J.Am.Chem.Soc.1997, vol.93, p.1517-1522; WO 2006/114966 A1).
By the hydrogen peroxide of 2-hexyloxy-7-m-ethyl aniline base-thioxanthone and 30%, the ratio take mol ratio as 1:1 is dissolved in acetic acid, in 100 ℃ of backflows, the cooling precipitation of separating out, filter and use ethyl alcohol recrystallization, must be oxidized thioxanthone analog derivative Comp-27, productive rate is about 90%.m/z：463.18(100.0%)，464.19(29.7%)，465.19(5.0%)，465.18（0.8%）。
Embodiment 28
Synthetic oxidation thioxanthone analog derivative Comp-28
Figure BDA00002372523900173
Synthesized reference document (Patent:GB932494,1958 of the own sulfydryl-7-of 2-cumic aldehyde amido-thioxanthone; Chem.Abstr.1964, vol.61,9477; WO 2006/114966 A1).
By the hydrogen peroxide of own 2-sulfydryl-7-cumic aldehyde amido-thioxanthone and 30%, be dissolved in acetic acid take mol ratio as the ratio of 1: 1, in 100 ℃ of backflows, the cooling precipitation of separating out, filter and use ethyl alcohol recrystallization, must be oxidized thioxanthone analog derivative Comp-28, productive rate is about 90%.m/z：493.17(100.0%)，494.18(30.8%)，495.18(9.3%)，495.19（1.0%）。
Embodiment 29
The derivative Comp-1 obtaining with embodiment 1 is prepared with organic electroluminescence devices:
Sheet glass supersound process in commercial clean-out system of ITO transparency conducting layer will be coated with, in deionized water, rinse, at acetone: ultrasonic oil removing in alcohol mixed solvent, under clean environment, be baked to and remove moisture content completely, irradiate 10 minutes with UV-light cleaning machine, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10 -5～9 × 10 -3pa, first evaporation CuPc15nm on above-mentioned anode tunic, continues evaporation NPB as hole transmission layer, and evaporation speed is that 0.1nm/s. evaporation thickness is 75nm;
On hole transmission layer, continue the Ir (ppy) of evaporation one deck Comp-1 doping 3as the organic luminous layer of device, Comp-1 and Ir (ppy) 3evaporation speed ratio be 1:100, Ir (ppy) 3doping content in Comp-1 is 7wt%, and the total speed of its evaporation is 0.1nm/s, and evaporation total film thickness is 30nm;
Continue the electron transfer layer of evaporation one deck TPBI as device, its evaporation speed is 0.lnm/s again, and evaporation total film thickness is 35nm;
Finally, on above-mentioned electron transfer layer, evaporation LiF layer and Mg:Ag alloy layer are as the cathode layer of device successively, and wherein the thickness of LiF layer is 0.5nm, and the evaporation speed of Mg:Ag alloy layer is 2.0～3.0nm/s, and thickness is 100nm.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy) 3comp-1 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows: tristimulus coordinates: (X=0.27, Y=0.63);
Play bright voltage: 3.5V;
High-high brightness: 11786cd/m 2(8.2V);
Luminous efficiency: 14.63cd/A.
Embodiment 30
Select the derivative Comp-3 that embodiment 3 obtains to be prepared with organic electroluminescence devices:
Except using Comp-3 to replace Comp-1, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy) 3: Comp-3 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.28, Y=0.63);
Play bright voltage: 3.2V;
High-high brightness: 11845cd/m 2(9.5V);
Luminous efficiency: 14.91cd/A.
Embodiment 31
Select the derivative Comp-5 that embodiment 5 obtains to be prepared with organic electroluminescence devices:
Except using Comp-5 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-5 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.15, Y=0.35);
Play bright voltage: 3.7V;
High-high brightness: 9995cd/m 2(9.1V);
Luminous efficiency: 21.47cd/A.
Embodiment 32
Select the derivative Comp-6 that embodiment 6 obtains to be prepared with organic electroluminescence devices:
Except using Comp-6 to replace Comp-1, Ir (piq) 3replace Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/5wt%Ir (piq) 3: Comp-6 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.66, Y=0.33);
Play bright voltage: 4.2V;
High-high brightness: 8720cd/m 2(10.2V);
Luminous efficiency: 28.39cd/A.
Embodiment 33
Select the derivative Comp-7 that embodiment 7 obtains to be prepared with organic electroluminescence devices:
Except using Comp-7 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-7 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.14, Y=0.33);
Play bright voltage: 3.5V;
High-high brightness: 8776cd/m 2(8.8V);
Luminous efficiency: 19.82cd/A.
Embodiment 34
Select the derivative Comp-8 that embodiment 8 obtains to be prepared with organic electroluminescence devices:
Except using Comp-8 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-8 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.15, Y=0.34);
Play bright voltage: 3.7V;
High-high brightness: 8835cd/m 2(9.4V);
Luminous efficiency: 15.43cd/A.
Embodiment 35
Select the derivative Comp-10 that embodiment 10 obtains to be prepared with organic electroluminescence devices:
Except using Comp-10 to replace Comp-1, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy) 3: Comp-10 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.28, Y=0.64);
Play bright voltage: 3.1V;
High-high brightness: 12642cd/m 2(9.6V);
Luminous efficiency: 25.69cd/A.
Embodiment 36
Select the derivative Comp-12 that embodiment 12 obtains to be prepared with organic electroluminescence devices:
Except using Comp-12 to replace Comp-1, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy) 3: Comp-12 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.27, Y=0.65);
Play bright voltage: 4.4V;
High-high brightness: 10578cd/m 2(8.8V);
Luminous efficiency: 16.83cd/A.
Embodiment 37
Select the derivative Comp-14 that embodiment 14 obtains to be prepared with organic electroluminescence devices:
Except using Comp-14 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-14 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.15, Y=0.37);
Play bright voltage: 3.7V;
High-high brightness: 11465cd/m 2(8.7V);
Luminous efficiency: 26.83cd/A.
Embodiment 38
Select the derivative Comp-16 that embodiment 16 obtains to be prepared with organic electroluminescence devices:
Except using Comp-16 to replace Comp-1, Ir (piq) 3replace Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/5wt%Ir (piq) 3: Comp-16 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.66, Y=0.32);
Play bright voltage: 4.5V;
High-high brightness: 8733cd/m 2(9.3V);
Luminous efficiency: 27.23cd/A.
Embodiment 39
Select the derivative Comp-18 that embodiment 18 obtains to be prepared with organic electroluminescence devices:
Except using Comp-18 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-18 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.15, Y=0.33);
Play bright voltage: 3.5V;
High-high brightness: 8671cd/m 2(8.7V);
Luminous efficiency: 16.37cd/A.
Embodiment 40
Select the derivative Comp-19 that embodiment 19 obtains to be prepared with organic electroluminescence devices:
Except using Comp-19 to replace Comp-1, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy) 3: Comp-19 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.27, Y=0.64);
Play bright voltage: 3.4V;
High-high brightness: 12575cd/m 2(8.3V);
Luminous efficiency: 23.88cd/A.
Embodiment 41
Select the derivative Comp-21 that embodiment 21 obtains to be prepared with organic electroluminescence devices:
Except using Comp-21 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-21 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.13, Y=0.30);
Play bright voltage: 3.9V;
High-high brightness: 8327cd/m 2(9.3V);
Luminous efficiency: 17.73cd/A.
Embodiment 42
Select the derivative Comp-22 that embodiment 22 obtains to be prepared with organic electroluminescence devices:
Except using Comp-22 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-22 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.15, Y=0.34);
Play bright voltage: 4.1V;
High-high brightness: 7548cd/m 2(9.9V);
Luminous efficiency: 15.53cd/A.
Embodiment 43
Select the derivative Comp-24 that embodiment 24 obtains to be prepared with organic electroluminescence devices:
Except using Comp-24 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-24 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.14, Y=0.32);
Play bright voltage: 3.0V;
High-high brightness: 8376cd/m 2(8.1V);
Luminous efficiency: 18.01cd/A.
Embodiment 44
Select the derivative Comp-25 that embodiment 25 obtains to be prepared with organic electroluminescence devices:
Except using Comp-25 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-25 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.14, Y=0.29);
Play bright voltage: 3.8V;
High-high brightness: 7970cd/m 2(10.3V);
Luminous efficiency: 17.84cd/A.
Embodiment 45
Select the derivative Comp-28 that embodiment 28 obtains to be prepared with organic electroluminescence devices:
Except using Comp-28 to replace Comp-1, FIrpic replaces Ir (ppy) 3in addition, according to the step identical with embodiment 29, prepare the performance of organic EL device test component.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-28 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1 100nm)
Device performance index is as follows:
Tristimulus coordinates: (X=0.13, Y=0.31);
Play bright voltage: 3.8V;
High-high brightness: 8451cd/m 2(9.5V);
Luminous efficiency: 18.26cd/A.
Embodiment 46
The preparation method of oxidation thioxanthone analog derivative, comprises the following steps:
A, ratio by the nitrate solution of thioxanthone compounds and concentration 0.001M take mol ratio as 1:0.1 are dissolved in acetonitrile, stir, and add water precipitation, filter, and filtrate recrystallization, obtains the oxidation thioxanthone analog derivative shown in formula (1);
B, by thioxanthone compounds and hydrogen peroxide solution, the ratio take mol ratio as 1:0.1 is dissolved in acetic acid, refluxes, and the cooling precipitation of separating out, filters, and filtrate recrystallization, obtains being oxidized thioxanthone analog derivative shown in formula (2);
The structural formula of described thioxanthone compounds is:
In formula, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be respectively hydrogen atom, neopentyl oxygen, positive butylthio, diisoamyl amido, o-, m-, p-isopropyl phenyl amido, phenoxy group, thiophenyl, 9,9 '-dimethyl fluorenyl; Described nitrate solution is sodium nitrate solution; The solvent that described recrystallization is selected is methyl alcohol; Described backflow is to reflux under 25 ℃ of conditions.
Embodiment 47
With embodiment 46, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be respectively o-, m-, p-aminomethyl phenyl amido, two (o-, m-, p-isopropyl phenyl) amido, two (o-, m-, p-iodine substituted phenyl) amido, pyrenyl, 9,9 '-spiral shell, two fluorenyls, 1-pyrryl, 5-pseudoindoyl, 1-isobenzofuran-base;
Described nitrate solution is ammonium nitrate solution; The solvent that described recrystallization is selected is the mixed solvent of methylene dichloride and methyl-sulphoxide; Described backflow is to reflux under 50 ℃ of conditions.
Embodiment 48
With embodiment 46, difference is: R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be respectively 1,8-phenanthrene and cough up beautiful jade-2-base, 1,9-phenanthrene is coughed up beautiful jade-7-base, 1, and 10-phenanthrene is coughed up beautiful jade-5-base, 2, and 8-phenanthrene is coughed up beautiful jade-3-base, lysivane base, 2-methylpyrrole-5-base, 2-tertiary butyl pyrroles-4-base, 5-oxadiazolyl;
Described nitrate solution is iron nitrate solution; The solvent that described recrystallization is selected is diformamide.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.

Claims (10)

1. oxidation thioxanthone analog derivative, is characterized in that, its structural formula is as follows:
Figure FDA00002372523800011
In formula (1) and formula (2), R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be selected from respectively the one in hydrogen atom, alkoxyl group, alkylthio, alkylamino radical, aryl amine, aryloxy, arylthio, aryl, heteroaromatic group, and R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8in have one at least for aromatic group.
2. according to the oxidation thioxanthone analog derivative of claim 1, it is characterized in that,
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkoxyl group being selected from is the alkoxyl group of 1 to 20 carbon atom;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkylthio being selected from is the alkylthio of 1 to 20 carbon atom;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkylamino radical being selected from is not substituted alkyl amido or the substituted alkyl amido of 1 to 20 carbon atom;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the aryl amine being selected from is the aryl amine of 6 to 30 carbon atoms;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the aryloxy being selected from is phenoxy group;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the arylthio being selected from is thiophenyl;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the aryl being selected from is aryl or the substituted aryl of 6 to 30 carbon atoms;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the hetero-aromatic ring being selected from is the fragrant heterocycle of 5 to 50 annular atomses or the fragrant heterocycle of replacement.
3. according to the oxidation thioxanthone analog derivative of claim 1, it is characterized in that,
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkoxyl group of 1 to 20 carbon atom being selected from is: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy, neopentyl oxygen, tertiary pentyloxy, hexyloxy, 2-methyl pentyloxy;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkylthio of 1 to 20 carbon atom being selected from is: methylthio group, ethylmercapto group, rosickyite base, positive butylthio, secondary butylthio, tertiary butylthio;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the alkylamino radical of 1 to 20 carbon atom being selected from is: methylamino, ethylamino-, Propylamino, butylamine base, amylamine base, isoamyl amido, neopentyl amine base, tertiary amylamine base, hexylamine base, dimethylin, diethylin, dipropyl amido, dibutyl amino, diamyl amido, diisoamyl amido, two neopentyl amine bases, two tertiary amylamine bases, dihexylamine base;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the aryl amine of 6 to 30 carbon atoms that are selected from is: o-, m-, and p-aminomethyl phenyl amido, o-, m-, p-ethylphenyl amido, o-, m-, p-propyl group phenyl amido, o-, m-, p-isopropyl phenyl amido, o-, m-, p-p-methoxy-phenyl amido, o-, m-, p-ethoxyl phenenyl amido, o-, m-, p-propoxy-phenyl amido, o-, m-, p-difluorophenyl amido, o-, m-, p-chlorophenyl amido, o-, m-, p-bromo phenyl amido, o-, m-, p-iodine substituted phenyl amido, two (o-, m-, p-aminomethyl phenyl) amido, two (o-, m-, p-ethylphenyl) amido, two (o-, m-, p-propyl group phenyl) amido, two (o-, m-, p-isopropyl phenyl) amido, two (o-, m-, p-p-methoxy-phenyl) amido, two (o-, m-, p-ethoxyl phenenyl) amido, two (o-, m-, p-propoxy-phenyl) amido, two (o-, m-, p-difluorophenyl) amido, two (o-, m-, p-chlorophenyl) amido, two (o-, m-, p-bromo phenyl) amido, two (o-, m-, p-iodine substituted phenyl) amido,
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the aryl of 6 to 30 carbon atoms that are selected from is: phenyl, phenylbenzene, triphenyl, naphthacenyl, pyrenyl, fluorenes, spiral shell fluorenes;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the substituted aryl of 6 to 30 carbon atoms that are selected from is: o-, m-, and p-tolyl, xylyl, o-, m-, p-cumyl, trimethylphenyl, 9,9 '-dimethyl fluorenyl, 9,9 '-spiral shell, two fluorenyls;
Described R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8the fragrant heterocycle of 5 to 50 annular atomses that are selected from is: 1-pyrryl, 2-pyrryl, 3-pyrryl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indyl, 2-indyl, 3-indyl, 4-indyl, 5-indyl, 6-indyl, 7-indyl, 1-pseudoindoyl, 2-pseudoindoyl, 3-pseudoindoyl, 4-pseudoindoyl, 5-pseudoindoyl, 6-pseudoindoyl, 7-pseudoindoyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl, diphenylene-oxide-2-base, 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base, 7-isobenzofuran-base, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 1-carbazyl, 2-carbazyl, 3-carbazyl, 4-carbazyl, 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, 1-acridyl, 2-acridyl, 3-acridyl, 4-acridyl, 9-acridyl, 1,7-phenanthrene is coughed up beautiful jade-2-base, 1,7-phenanthrene is coughed up beautiful jade-3-base, 1,7-phenanthrene is coughed up beautiful jade-4-base, 1,7-phenanthrene is coughed up beautiful jade-5-base, 1,7-phenanthrene is coughed up beautiful jade-6-base, 1,7-phenanthrene is coughed up beautiful jade-8-base, 1,7-phenanthrene is coughed up beautiful jade-9-base, 1,7-phenanthrene is coughed up beautiful jade-10-base, 1,8-phenanthrene is coughed up beautiful jade-2-base, 1,8-phenanthrene is coughed up beautiful jade-3-base, 1,8-phenanthrene is coughed up beautiful jade-4-base, 1,8-phenanthrene is coughed up beautiful jade-5-base, 1,8-phenanthrene is coughed up beautiful jade-6-base, 1,8-phenanthrene is coughed up beautiful jade-7-base, 1,8-phenanthrene is coughed up beautiful jade-9-base, 1,8-phenanthrene is coughed up beautiful jade-10-base, 1,9-phenanthrene is coughed up beautiful jade-2-base, 1,9-phenanthrene is coughed up beautiful jade-3-base, 1,9-phenanthrene is coughed up beautiful jade-4-base, 1,9-phenanthrene is coughed up beautiful jade-5-base, 1,9-phenanthrene is coughed up beautiful jade-6-base, 1,9-phenanthrene is coughed up beautiful jade-7-base, 1,9-phenanthrene is coughed up beautiful jade-8-base, 1,9-phenanthrene is coughed up beautiful jade-10-base, 1,10-phenanthrene is coughed up beautiful jade-2-base, 1,10-phenanthrene is coughed up beautiful jade-3-base, 1,10-phenanthrene is coughed up beautiful jade-4-base, 1,10-phenanthrene is coughed up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2,9-phenanthrolines-3-base, 2,9-phenanthrolines-4-base, 2,9-phenanthrolines-5-base, 2,9-phenanthrolines-6-base, 2,9-phenanthrolines-7-base, 2,9-phenanthrolines-8-base, 2,9-phenanthrolines-10-base, 2,8-phenanthrene is coughed up beautiful jade-1-base, 2,8-phenanthrene is coughed up beautiful jade-3-base, 2,8-phenanthrene is coughed up beautiful jade-4-base, 2,8-phenanthrene is coughed up beautiful jade-5-base, 2,8-phenanthrene is coughed up beautiful jade-6-base, 2,8-phenanthrene is coughed up beautiful jade-7-base, 2,8-phenanthrene is coughed up beautiful jade-9-base, 2,8-phenanthrene is coughed up beautiful jade-10-base, 2,7-phenanthrene is coughed up beautiful jade-1-base, 2,7-phenanthrene is coughed up beautiful jade-3-base, 2,7-phenanthrene is coughed up beautiful jade-4-base, 2,7-phenanthrene is coughed up beautiful jade-5-base, 2,7-phenanthrene is coughed up beautiful jade-6-base, 2,7-phenanthrene is coughed up beautiful jade-8-base, 2,7-phenanthrene is coughed up beautiful jade-9-base, 2,7-phenanthrene is coughed up beautiful jade-10-base, 1-phenazinyl, 2-phenazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, lysivane base, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazan base, 2-thienyl, 3-thienyl, dibenzothiophene-2-base, 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tertiary butyl pyrroles-4-base, 3-(2-phenyl propyl) pyrroles one-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tertiary butyl-1-indyl, the 4-tertiary butyl-1-indyl, the 2-tertiary butyl-3-indyl, the 4-tertiary butyl-3-indyl.
4. the preparation method of the oxidation thioxanthone analog derivative as described in as arbitrary in claim 1 ~ 3, is characterized in that, comprises the following steps:
A, by thioxanthone compounds and concentration, higher than the nitrate solution of 10M, the ratio take mol ratio as 1:0.1 ~ 100 is not dissolved in acetonitrile, stirs, and adds water precipitation, filters, and filtrate recrystallization, obtains the oxidation thioxanthone analog derivative shown in formula (1); Or
B, by thioxanthone compounds and hydrogen peroxide solution, the ratio take mol ratio as 1:0.1 ~ 100 is dissolved in acetic acid, refluxes, and the cooling precipitation of separating out, filters, and filtrate recrystallization, obtains being oxidized thioxanthone analog derivative shown in formula (2).
5. the preparation method of oxidation thioxanthone analog derivative according to claim 4, is characterized in that, the structural formula of described thioxanthone compounds is:
In formula, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8be selected from respectively the one in hydrogen atom, alkoxyl group, alkylthio, alkylamino radical, aryl amine, aryloxy, arylthio, aryl, heteroaromatic group, and R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8in have one at least for aromatic group.
6. the preparation method of oxidation thioxanthone analog derivative according to claim 4, is characterized in that, described nitrate solution is SODIUMNITRATE, ammonium nitrate, iron nitrate or nitrous acid ferrous solution; The solvent that described recrystallization is selected is one or more mixed solvents in methyl alcohol, ethanol, methylene dichloride, methyl-sulphoxide, diformamide; Described backflow is to reflux under 25～100 ℃ of conditions.
7. the application of the oxidation thioxanthone analog derivative as described in as arbitrary in claim 1 ~ 6, is characterized in that, this oxidation thioxanthone analog derivative can be used as the organic luminous layer of organic electroluminescence device.
8. the application of oxidation thioxanthone analog derivative according to claim 7, is characterized in that, described oxidation thioxanthone analog derivative can be made electrophosphorescence device by Doping Phosphorus photoinitiator dye.
9. the application of oxidation thioxanthone analog derivative according to claim 8, is characterized in that, the doping content of phosphorescent coloring is 5 ~ 15wt%.
10. the application of oxidation thioxanthone analog derivative according to claim 9, is characterized in that, the structure of described organic electroluminescence device is: substrate/anode/hole transmission layer/organic luminous layer/electron transfer layer/negative electrode; Substrate is a kind of material in glass, polyester, poly-phthalimide compounds; Anode is a kind of material in tin indium oxide, zinc oxide, zinc tin oxide, gold and silver, copper, Polythiophene/polyvinylbenzenesulfonic acid sodium, polyaniline; Negative electrode is lithium, magnesium, calcium, strontium, aluminium or indium, or a kind of and copper, gold or silver-colored alloy in them, or the electrode layer that alternately forms of above-mentioned metal or alloy and metal fluoride; Hole transmission layer is tri-arylamine group material; Electron transfer layer is nitrogen heterocycles material; Organic luminous layer is the oxidation thia anthracyclinone derivatives shown in formula (1) or (2).
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* Cited by examiner, † Cited by third party
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WO2016149975A1 (en) * 2015-03-26 2016-09-29 深圳市华星光电技术有限公司 Thioxanthone-aromatic amine compound and organic light-emitting device applying same
CN107068876A (en) * 2016-04-25 2017-08-18 中节能万润股份有限公司 A kind of organic electroluminescence device and its application based on 10,10- diaryl anthracene assimilation compounds
WO2018014405A1 (en) * 2016-07-20 2018-01-25 深圳市华星光电技术有限公司 Light-emitting material, preparation method therefor and organic light-emitting diode using same
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050234031A1 (en) * 2004-02-04 2005-10-20 Schrimpf Michael R Amino-substituted tricyclic derivatives and methods of use
JP2006098699A (en) * 2004-09-29 2006-04-13 Kyocera Mita Corp Thioxanthene derivative and electrophotographic photoreceptor using the same
US20060194147A1 (en) * 2005-02-18 2006-08-31 Fuji Photo Film Co., Ltd. Resist composition, compound for use in the resist composition and pattern forming method using the resist composition
WO2012063751A1 (en) * 2010-11-08 2012-05-18 Canon Kabushiki Kaisha Thioxanthone compound and organic light emitting element having the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050234031A1 (en) * 2004-02-04 2005-10-20 Schrimpf Michael R Amino-substituted tricyclic derivatives and methods of use
JP2006098699A (en) * 2004-09-29 2006-04-13 Kyocera Mita Corp Thioxanthene derivative and electrophotographic photoreceptor using the same
US20060194147A1 (en) * 2005-02-18 2006-08-31 Fuji Photo Film Co., Ltd. Resist composition, compound for use in the resist composition and pattern forming method using the resist composition
WO2012063751A1 (en) * 2010-11-08 2012-05-18 Canon Kabushiki Kaisha Thioxanthone compound and organic light emitting element having the same

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KIUMARS BAHRAMI ET AL.: "TMSCl-promoted selective oxidation of sulfides to sulfoxides with hydrogen peroxide", 《TETRAHEDRON LETTERS》 *
PEDRO M. J. LORY ET AL.: "Synthesis and screening of 3-substituted thioxanthen-9-one-10,10-dioxides", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 *
SAMIA AMRIOU ET AL.: "The Interplay of Inverted Redox Potentials and Aromaticity in the Oxidized States of New π-Electron Donors: 9-(1,3-Dithiol-2-ylidene)fluorene and 9-(1,3-Dithiol-2-ylidene)thioxanthene Derivatives", 《CHEM. EUR. J.》 *
Y.-B. HUANG ET AL.: "A recyclable fluorous thiourea organocatalyst for the chemoselective oxidation of sulfides", 《JOURNAL OF FLUORINE CHEMISTRY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016149975A1 (en) * 2015-03-26 2016-09-29 深圳市华星光电技术有限公司 Thioxanthone-aromatic amine compound and organic light-emitting device applying same
CN107068876A (en) * 2016-04-25 2017-08-18 中节能万润股份有限公司 A kind of organic electroluminescence device and its application based on 10,10- diaryl anthracene assimilation compounds
WO2018014405A1 (en) * 2016-07-20 2018-01-25 深圳市华星光电技术有限公司 Light-emitting material, preparation method therefor and organic light-emitting diode using same
WO2018014389A1 (en) * 2016-07-20 2018-01-25 深圳市华星光电技术有限公司 Light-emitting material, preparation method thereof and organic light-emitting diode using light-emitting material
CN109748916A (en) * 2017-11-03 2019-05-14 江苏三月光电科技有限公司 It is a kind of using azepine spiro fluorene and aryl ketones as the compound of core, preparation method and its application on OLED

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