CN108276325A - Electroluminescent organic material and preparation method thereof and organic electroluminescence device - Google Patents

Electroluminescent organic material and preparation method thereof and organic electroluminescence device Download PDF

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CN108276325A
CN108276325A CN201810111723.7A CN201810111723A CN108276325A CN 108276325 A CN108276325 A CN 108276325A CN 201810111723 A CN201810111723 A CN 201810111723A CN 108276325 A CN108276325 A CN 108276325A
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substituted
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姜志远
姜晓晨
贺金新
王进政
索红光
金福荣
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The present invention relates to a kind of electroluminescent organic material and preparation method thereof and organic electroluminescence devices, belong to luminescent material technical field.New structural electroluminescent organic material provided by the invention has chromaticity coordinates appropriate, and the luminous efficiency as organic electroluminescence device made from luminescent layer is high, device lifetime is good.There is electroluminescent organic material provided by the invention high electronics to convey efficiency, so as to prevent from crystallizing when manufacturing device, and can be readily formed layer, hence improve the current characteristics of device.The preparation method of electroluminescent organic material provided by the invention, raw material are easy to get, simple for process, are suitable for industrialized production.

Description

Electroluminescent organic material and preparation method thereof and organic electroluminescence device
Technical field
The present invention relates to luminescent material technical fields, and in particular to a kind of electroluminescent organic material and preparation method thereof and Organic electroluminescence device.
Background technology
Electroluminescent device is to be activated and luminous display device that it is as emissive type using electroluminescent material Display device has the advantage that visible angle is wide, good contrast and answer speed are fast.1987, Kodak developed for the first time Using low molecule aromatic diamines and aluminium complex as the organic electroluminescence device (OLED) of emitting layer material.
OLED have it is thin and lightweight, actively shine, wide viewing angle, quick response, low energy consumption, low temperature and anti-seismic performance it is excellent with And the advantages that potential flexible design.OLED is full solid-state device, no vacuum chamber, no liquid parts, so not being afraid of vibrations, is used It is convenient, in addition high resolution, the features such as visual angle is wide and operating temperature range is wide, will obtain in weaponry and adverse circumstances field To extensive use.In addition, OLED is alternatively arranged as planar backlight source and the lighting source application of display field.Therefore, OLED has Good development prospect, but OLED also needs to further improve in terms of service life and luminous efficiency there is also deficiency at present.
Invention content
The object of the present invention is to provide a kind of new structural electroluminescent organic material and preparation method thereof and Organic Electricities Electroluminescence device, the new structural electroluminescent organic material have chromaticity coordinates appropriate, have as made from luminescent layer The luminous efficiency of organic electroluminescence devices is high, device lifetime is good.
To achieve the goals above, technical scheme of the present invention is specific as follows：
A kind of electroluminescent organic material, chemical structural formula are as follows：
In formula, Ar1For total carbon atom number be 6-27 substituted or unsubstituted phenyl or total carbon atom number be 12-20's Substituted or unsubstituted aromatic heterocyclic radical or the substituted or unsubstituted fused ring aryl that total carbon atom number is 10-25；
Ar2For total carbon atom number be 6-21 substituted or unsubstituted phenyl or total carbon atom number be 4-20 substitution or Unsubstituted aromatic heterocyclic radical or the substituted or unsubstituted fused ring aryl that total carbon atom number is 10-15；
A is hydrogen or phenyl.
In the above-mentioned technical solutions, the Ar1The substituted or unsubstituted phenyl or total carbon for being 7-26 for total carbon atom number The substituted or unsubstituted aromatic heterocyclic radical or total carbon atom number that atomicity is 14-19 are the substituted or unsubstituted thick of 24-25 Cyclophane base.
In the above-mentioned technical solutions, the Ar1The substituted or unsubstituted phenyl or total carbon for being 9-21 for total carbon atom number Atomicity is the substituted or unsubstituted aromatic heterocyclic radical of 15-16, Ar2It is the substituted or unsubstituted of 8-18 for total carbon atom number The substitution that the substituted or unsubstituted aromatic heterocyclic radical or total carbon atom number that phenyl or total carbon atom number are 14-18 are 14-15 Or unsubstituted fused ring aryl.
In the above-mentioned technical solutions, the Ar1The substituted or unsubstituted phenyl for being 12-20 for total carbon atom number, Ar2For The substituted or unsubstituted aromatics that the substituted or unsubstituted phenyl or total carbon atom number that total carbon atom number is 11-16 are 15-16 Heterocycle.
In the above-mentioned technical solutions, the Ar1The substituted or unsubstituted phenyl for being 16-18 for total carbon atom number, Ar2For Total carbon atom number is the substituted or unsubstituted phenyl of 12-13.
In the above-mentioned technical solutions, the electroluminescent organic material is any one in following concrete structure：
A kind of preparation method of electroluminescent organic material, includes the following steps：
Compound a is dissolved in tetrahydrofuran, stirring 1 is small after hexane solvent, n-BuLi are added dropwise under the conditions of -78 DEG C When；Trimethylborate is added dropwise again, stirs 2h；Then it is added dropwise after hydrochloric acid neutralization, extracts product with ethyl acetate and water, use dichloro Methane and hexane are recrystallized to give compound b；
After compound b, compound c, tetra-triphenylphosphine palladium and potassium carbonate are dissolved in toluene/EtOH/ distilled water, 90 DEG C heating 2 hours；It being ground with methanol after organic layer vacuum distillation, obtained solid is dissolved in silica gel filtering after dichloromethane, It is ground to obtain compound d with dichloro hexane；
After triethyl phosphite and dichloro-benzenes is added in compound d, 150 DEG C are stirred overnight；Reaction is depressurized after terminating It is extracted with ethyl acetate after concentration and concentrates again, compound e is obtained with column chromatography；
By compound e, contain Ar1Bromide, cuprous iodide, ethylenediamine and the cesium carbonate of substituent group are sequentially added into toluene Return stirring afterwards, vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical compounds I later；
Chemical compounds I contains Ar2After bromide, cuprous iodide, ethylenediamine and the cesium carbonate of substituent group are dissolved in toluene, Return stirring one day, is extracted with ethyl acetate after vacuum distillation, dichloromethane/hexane crosses pillar and is recrystallized to give chemical formula again Electroluminescent organic material described in 1；
Synthetic route is as follows：
Wherein, Ar1For total carbon atom number be 6-27 substituted or unsubstituted phenyl or total carbon atom number be 12-20's Substituted or unsubstituted aromatic heterocyclic radical or the substituted or unsubstituted fused ring aryl that total carbon atom number is 10-25；
Ar2For total carbon atom number be 6-21 substituted or unsubstituted phenyl or total carbon atom number be 4-20 substitution or Unsubstituted aromatic heterocyclic radical or the substituted or unsubstituted fused ring aryl that total carbon atom number is 10-15；
A is hydrogen or phenyl.
A kind of organic electroluminescence device, including first electrode, second electrode and it is set to the first electrode and second Organic layer between electrode；The organic layer includes electroluminescent organic material shown in chemical formula 1.
In the above-mentioned technical solutions, the organic layer further includes by I main group, II main group, IV main group, V main group transfer gold Belong to, more than one metal or its metal complex in lanthanum and d- transfer elements.
The organic layer further includes the luminescent layer of other materials and electronically forms layer.
Above-mentioned electroluminescent organic material can be applied to organic photovoltaic cell, Electronic Paper, Organophotoreceptor, organic crystal Pipe or ink-jet printing material.
In addition, above-mentioned organic layer be comprising other than the more than one electroluminescent organic material, further include blue, it is red The organic luminous layer of color or yellow emitting compound is formed simultaneously white color organic electroluminescence device.
Another side inner surface chalkogenide in a face electrode is at least disposed in the organic electroluminescence device of the present invention (chalcogenide), one layer or more selected in halogenated metal layer and metal oxide layer.
Specifically the anode surface silicon of organic luminous layer, aluminium and chalkogenide (chalcogenide) (including oxide) Layer, in addition the cathode surface of illuminator layer side disposes halogen metal layer or metal oxide layer.It is driven from these implementations Stability.The ideal case of above-mentioned silicon, aluminium and chalkogenide is that have SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON or SiAlON, the ideal case of metal halide are that have LiF, MgF2, CAF2Or rare earth fluoride metalloid, the ideal of metal oxide are real Example is that have Cs2O, Li2O, MgO, SrO, BaO or CaO.
In addition, in the organic electroluminescence device of the present invention, electron transport compound, doped compound and sky are included at least One or more mixing in the transport compound of cave.
In the present invention, the methods of film vapor deposition, electron beam evaporation, physical vapour deposition (PVD) can be utilized to be deposited on substrate Metal, conductive oxide and their alloy form anode；The preparation method of cathode and anode preparation method one It causes；Hole injection layer, hole transmission layer, luminescent layer, air barrier and electricity are deposited in order in the cathode surface being prepared Sub- transport layer.In the present invention, hole injection layer, hole transmission layer, luminescent layer, hole blocking layer and electron transfer layer etc. are prepared High molecular material solvent engineering can be used during multilayered structure to be molded instead of spin-coating (spin-coating), strip (tape-casting), scraping blade method (doctor-blading), silk-screen printing (Screen-Printing), ink jet printing or heat It is imaged the preparation that evaporation coating methods such as (Thermal-Imaging) reduce the number of plies.
Organic electroluminescence material shown in formula 1 of the organic electroluminescence device provided by the invention using above-mentioned technical proposal Material is prepared.This organic electroluminescence device have preferable luminescent properties, can front shine, back side illuminated or two Face shines.
In the present invention, the organic electroluminescence device is preferred for organic photovoltaic cell (OSC), e-book (e- Paper), Organophotoreceptor (OPC) or polycrystalline organic thin film.
The beneficial effects of the invention are as follows：
New structural electroluminescent organic material provided by the invention has chromaticity coordinates appropriate, is used as luminescent layer system The luminous efficiency of the organic electroluminescence device obtained is high, device lifetime is good.
There is electroluminescent organic material provided by the invention high electronics to convey efficiency, so as to when manufacturing device It prevents from crystallizing, and layer can be readily formed, hence improve the current characteristics of device.
The preparation method of electroluminescent organic material provided by the invention, raw material are easy to get, simple for process, are suitable for industrializing Production.
Specific implementation mode
For a further understanding of the present invention, the organic electroluminescent that the representation compound of the present invention is illustrated the present invention Material and its manufacturing method and the characteristics of luminescence for illustrating the organic electroluminescence device prepared.
[synthesis example]
The synthesis of intermediate e：
Compound a (21g, 52.6mmol) is dissolved in tetrahydrofuran (300mL), and it is molten that hexane is added dropwise under the conditions of -78 DEG C Agent, 2.5M n-BuLis (25.2mL, 63.1mmol) stir a hour later.Slowly be added dropwise trimethylborate (18.2mL, 2h 79mmol) is stirred later.It is added dropwise after 2M hydrochloric acid neutralizes and extracts product with ethyl acetate and water.With dichloromethane and hexane weight Crystallization obtains compound b (8.4g, 47%).
By compound b (85.8g, 251mmol), compound c (50.7g, 251mmol), tetra-triphenylphosphine palladium (11g, 10mmol) and potassium carbonate (84.2g, 609mmol) is dissolved in toluene (1L)/EtOH (200mL)/distilled water (200mL) later 90 DEG C heating 2 hours.It is ground with methanol after organic layer vacuum distillation.Obtained solid is dissolved in silica gel mistake after dichloromethane Filter, is ground to obtain compound d (99.7g, 80%) with dichloro hexane.
Compound d (38.7g, 78mmol) is added to after triethyl phosphite (200mL) and dichloro-benzenes (150mL) A whole night is stirred at 150 DEG C.Reaction is extracted with ethyl acetate after being concentrated under reduced pressure after terminating and concentrates again, in being obtained with column chromatography Mesosome e (18.55g, 55%).
The synthesis of compound 4
By intermediate e (17.7g, 41mmol), 2- bromonaphthalenes (12.7g, 61.5mmol), cuprous iodide (3.9g, 20.5m Mol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) be sequentially added into toluene (250m L) with Return stirring afterwards.Be extracted with ethyl acetate dichloromethane and hexane after vacuum distillation cross pillar obtain compound 4-1 (19.0g, 83%).
By compound 4-1 (13.3g, 30.75mmol), 2- bromonaphthalenes (10.7g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) and return later Stream stirring one day.Dichloromethane/hexane crosses pillar and is recrystallized to give compound 4 again after vacuum distillation is extracted with ethyl acetate (17g, 75%), MS/FAB 684.24, calculated value 684.26.
The synthesis of compound 6
By intermediate e (17.7g, 41mmol), 1- (4- bromophenyls) naphthalene (17.3g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene (250mL) In after return stirring.Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain compound 6-1 later (21.6g, 83%).
By compound 6-1 (13.3g, 30.75mmol), 1- (4- bromophenyls) naphthalene (10.7g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) Later return stirring one day.Dichloromethane/hexane crosses pillar being recrystallized to give again after vacuum distillation is extracted with ethyl acetate Close object 6 (19.29g, 75%), MS/FAB 836.30, calculated value 836.32.
The synthesis of compound 9
By the bromo- 1,1'- biphenyl (14.3g, 61.5mmol) of intermediate e (17.7g, 41mmol), 4-, cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene (250mL) In after return stirring.Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain compound 9-1 later (19.9g, 83%).
The bromo- 1,1'- biphenyl (10.7g, 46.13mmol) of compound 9-1 (17.97g, 30.75mmol), 3-, iodate is sub- Copper (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene Return stirring one day later (200mL).Dichloromethane/hexane is crossed pillar and is recrystallized again after vacuum distillation is extracted with ethyl acetate Obtain compound 9 (17g, 75%), MS/FAB 736, calculated value 736.29.
The synthesis of compound 11
By the bromo- 2- methylbenzenes (10.45g, 61.5mmol) of intermediate e (17.7g, 41mmol), 1-, cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene (250mL) In after return stirring.Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain compound 11-1 later (17.78g, 83%).
By the bromo- 1,3- dimethyl benzenes (10.7g, 46.13mmol) of compound 11-1 (16.06g, 30.75mmol), 2-, iodine Change cuprous (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) and is added to toluene Return stirring one day later (200mL).Dichloromethane/hexane is crossed pillar and is recrystallized again after vacuum distillation is extracted with ethyl acetate Obtain compound 11 (17g, 75%), MS/FAB 626.25, calculated value 626.28.
The synthesis of compound 13
By the bromo- 1,1'- biphenyl (12.7g, 61.5mmol) of intermediate e (17.7g, 41mmol), 2-, cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene (250mL) In after return stirring.Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain compound 13-1 later (19.9g, 83%).
By compound 13-1 (17.97g, 30.75mmol), 9- bromines luxuriant and rich with fragrance (10.7g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) and return later Stream stirring one day.Dichloromethane/hexane crosses pillar and is recrystallized to give compound 13 again after vacuum distillation is extracted with ethyl acetate (17.53g, 75%), MS/FAB 760.27, calculated value 760.29.
The synthesis of compound 14
By intermediate e (17.7g, 41mmol), bromobenzene (9.59g, 61.5mmol), cuprous iodide (3.9g, 20.5mmo L) it is returned after, ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene (250mL) Stream stirring.Be extracted with ethyl acetate dichloromethane and hexane after vacuum distillation cross pillar obtain compound 14-1 (17.29g, 83%).
By the bromo- 9,9- dimethyl -9H- fluorenes of compound 4-1 (15.65g, 30.75mmol), 2- (12.55g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) it is added to toluene (200mL) return stirring one day later.Vacuum distillation dichloromethane later is extracted with ethyl acetate Alkane/hexane crosses pillar and is recrystallized to give compound 14 (16.15g, 75%), MS/FAB 700.25 again, and calculated value is 700.29。
The synthesis of compound 15
By bromo- two fluorenes of 9,9'- spiral shells (24.23g, 61.5mmol) of intermediate e (17.7g, 41mmol), 2-, cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene Return stirring after in (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical combination later Object 15-1 (25.40g, 83%).
By compound 15-1 (22.95g, 30.75mmol), bromobenzene (7.19g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) and return later Stream stirring one day.Dichloromethane/hexane crosses pillar and is recrystallized to give compound 15 again after vacuum distillation is extracted with ethyl acetate (18.96g, 75%), MS/FAB 822.29, calculated value 822.31.
The synthesis of compound 16
By bromo- 6,6,12,12- tetramethyls -6,12- indanes [1,2-b] fluorenes of intermediate e (17.7g, 41mmol), 2- (23.87g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, Return stirring after 123mmol) being sequentially added into toluene (250mL).Vacuum distillation dichloro later is extracted with ethyl acetate Methane and hexane cross pillar and obtain compound 16-1 (30.35g, 83%).
By compound 16-1 (13.3g, 30.75mmol), bromobenzene (10.7g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) and return later Stream stirring one day.Dichloromethane/hexane crosses pillar and is recrystallized to give compound 15 again after vacuum distillation is extracted with ethyl acetate (18.82g, 75%), MS/FAB 816.20, calculated value 816.35.
The synthesis of compound 17
By bromo- 1,1', 3', 1 "-terphenyl (18.94g, 61.5mmol) of intermediate e (17.7g, 41mmol), 3-, iodate Cuprous (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into first Return stirring after in benzene (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar later Close object 17-1 (22.47g, 83%).
By bromo- 1,1', 3', 1 "-terphenyl of compound 17-1 (20.30g, 30.75mmol), 3- (14.21g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) it is added to toluene (200mL) return stirring one day later.Vacuum distillation dichloromethane later is extracted with ethyl acetate Alkane/hexane crosses pillar and is recrystallized to give compound 17 (20.49g, 75%), MS/FAB 888.31 again, and calculated value is 888.35。
The synthesis of compound 18
By the bromo- 9- phenyl -9H- carbazoles (12.58g, 39.2mmol) of compound 9-1 (11.3g, 26.13mmol), 3-, iodine Change cuprous (2.5g, 13.1mmol), ethylenediamine (0.94mL, 17.4mmol), cesium carbonate (25.5g, 78.5mmol) are added to first Benzene (180mL) return stirring one day later.Distillation under pressure after being extracted with ethyl acetate.Dichloromethane/hexane is crossed pillar and is weighed again Crystallization obtains compound 18 (10.6g, 65%).MS/FAB is 825, calculated value 825.3.
The synthesis of compound 19
By intermediate e (17.7g, 41mmol), (4- bromophenyls) silane (14.02g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene Return stirring after in (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical combination later Object 19-1 (19.75g, 83%).
By compound 19-1 (17.84g, 30.75mmol), bromobenzene (7.19g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) and return later Stream stirring one day.Dichloromethane/hexane crosses pillar and is recrystallized to give compound 19 again after vacuum distillation is extracted with ethyl acetate (15.13g, 75%), MS/FAB 656.20, calculated value 656.26.
The synthesis of compound 20
By intermediate e (17.7g, 41mmol), 4- bromobenzenes simultaneously [b, d] furans (15.13g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene Return stirring after in (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical combination later Object 20-1 (20.36g, 83%).
By the bromo- 1,1'- xenyls (10.70g, 46.13mmol) of compound 20-1 (18.39g, 30.75mmol), 4-, iodine Change cuprous (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) and is added to toluene Return stirring one day later (200mL).Dichloromethane/hexane is crossed pillar and is recrystallized again after vacuum distillation is extracted with ethyl acetate Obtain compound 20 (23.07g, 75%), MS/FAB 750.25, calculated value 750.27.
The synthesis of compound 21
By intermediate e (17.7g, 41mmol), bromobenzene (9.59g, 61.5mmol), cuprous iodide (3.9g, 20.5mmo L) it is returned after, ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene (250mL) Stream stirring.Be extracted with ethyl acetate dichloromethane and hexane after vacuum distillation cross pillar obtain compound 21-1 (17.29g, 83%).
By compound 21-1 (15.63g, 30.75mmol), 4- Bromopyrimidines (7.29g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) Later return stirring one day.Dichloromethane/hexane crosses pillar being recrystallized to give again after vacuum distillation is extracted with ethyl acetate Close object 21 (13.51g, 75%), MS/FAB 586.20, calculated value 586.22.
The synthesis of compound 22
By the bromo- 4,6- diphenylpyrimidins (19.07g, 61.5mmol) of intermediate e (17.7g, 41mmol), 2-, cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene Return stirring after in (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical combination later Object 22-1 (22.54g, 83%).
By compound 22-1 (20.36g, 30.75mmol), bromobenzene (7.19g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) and return later Stream stirring one day.Dichloromethane/hexane crosses pillar and is recrystallized to give compound 22 again after vacuum distillation is extracted with ethyl acetate (17.03g, 75%), MS/FAB 738.25, calculated value 738.28.
The synthesis of compound 24
By the chloro- 4,6- diphenyl -1,3,5- triazines (5.07g, 19mmol) of compound 9-1 (9.4g, 16mmol), 2-, N, Dinethylformamide (1mL) mixes and 60% sodium hydride (0.8g, 20mmol) is added at room temperature later, stirring 12 hours, then It is filtered under diminished pressure after adding water.Obtained solid is ground with methanol/ethyl acetate, and silica gel is crossed after being dissolved again with methylene chloride Filtering, then grind to obtain compound 24 (11.5g, 88%).MS/FAB is 815, calculated value 815.3.
The synthesis of compound 29
Under a nitrogen atmosphere, in 500mL reaction vessels plus 11.6g (19.8mmol) compounds 9-1, compound 2- (3- Bromophenyl) -4,6- diphenyl -1,3,5- triazoles (9.2g, 23.8mmol) and sodium tert-butoxide (3.2g, 33.7mmol), first is used in combination Benzene (160mL) dissolves, and palladium dibenzylidene (0.454g, 0.5mmol) and tertiary butyl phosphine (0.6g, 1.49mmol) is added dropwise, and reaction is molten Liquid stirs 12 hours for 110 DEG C under a nitrogen atmosphere, and after reaction terminates plus methanol solvate obtains solid matter.Solid matter filters It is re-dissolved in chlorobenzene later, then adds activated carbon and anhydrous magnesium sulfate stirring.It is molten using chlorobenzene and methanol after solvent filter Agent is recrystallized to give compound 29 (12.9g, yield 73%).MS/FAB is 891, calculated value 891.34.
The synthesis of compound 33
Under a nitrogen atmosphere, by the chloro- 4- phenylquinazolines of compound 9-1 (11.5g, 19.75mmol) and 2- under room temperature (5.7g, 23.7mmol) is dissolved in dimethylbenzene (105mL) and stirs afterwards, add tris(dibenzylideneacetone) dipalladium (0.75g, 0.79mmol), sodium tert-butoxide (2.85g, 29.63mmol), tri-tert-butylphosphine (0.77ml, 1.58mmol) stir 6h later.Instead It is cooled to room temperature after should terminating, crosses filter solid, solid is dissolved in celite separating and filtering after dichloromethane.Filter to obtain solid Put that toluene (175mL) is inner to be dissolved by heating.Solid filtration drying after room temperature cooling, utilizes dichloromethane：Hexane=1:1 crosses pillar Obtain compound 33 (12.6g, 81%).MS/FAB is 788, calculated value 788.29.
The synthesis of compound 36
By intermediate e (17.7g, 41mmol), 2- (4- bromophenyls) -4- phenylquinazolines (22.14g, 61.5mmol), iodine Change cuprous (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) to be sequentially added into Return stirring after in toluene (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane are crossed pillar and are obtained later Compound 36-1 (24.31g, 83%).
By compound 36-1 (21.90g, 30.75mmol), bromobenzene (7.19g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene (200mL) and return later Stream stirring one day.Dichloromethane/hexane crosses pillar and is recrystallized to give compound 36 again after vacuum distillation is extracted with ethyl acetate (18.18g, 75%), MS/FAB 788.25, calculated value 788.29.
The synthesis of compound 39
By intermediate e (17.7g, 41mmol), 4- ([1,1'- xenyls] -4-yl) -2- (3- bromophenyls) quinoline (26.82g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, Return stirring after 123mmol) being sequentially added into toluene (250mL).Vacuum distillation dichloro later is extracted with ethyl acetate Methane and hexane cross pillar and obtain compound 39-1 (26.83g, 83%).
The bromo- 1,1'- biphenyl (7.19g, 46.13mmol) of compound 39-1 (24.23g, 30.75mmol), 4-, iodate is sub- Copper (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (21.41g, 92.3mmol) are added to toluene Return stirring one day later (200mL).Dichloromethane/hexane is crossed pillar and is recrystallized again after vacuum distillation is extracted with ethyl acetate Obtain compound 39 (21.75g, 75%), MS/FAB 940.34, calculated value 940.36.
The synthesis of compound 52
By the bromo- 4,6- diphenylpyrimidins (19.07g, 61.5mmol) of intermediate e (17.7g, 41mmol), 2-, cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene Return stirring after in (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical combination later Object 52-1 (22.54g, 83%).
By the bromo- 4,6- diphenylpyrimidins (14.30g, 46.13mmol) of compound 52-1 (20.36g, 30.75mmol), 2-, Cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to first Benzene (200mL) return stirring one day later.Dichloromethane/hexane is crossed pillar and is tied again again after vacuum distillation is extracted with ethyl acetate Crystalline substance obtains compound 52 (20.58g, 75%), MS/FAB 892.30, calculated value 892.33.
The synthesis of compound 53
By the bromo- 4,6- diphenyl -1,3,5- triazoles (19.13g, 61.5mmol) of intermediate e (17.7g, 41mmol), 2-, Cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into The return stirring to after in toluene (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane are crossed pillar and are obtained later To compound 53-1 (22.57g, 83%).
By the bromo- 4,6- diphenyl -1,3,5- triazoles of compound 53-1 (20.40g, 30.75mmol), 2- (14.35g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) it is added to toluene (200mL) return stirring one day later.Vacuum distillation dichloromethane later is extracted with ethyl acetate Alkane/hexane crosses pillar and is recrystallized to give compound 53 (20.63g, 75%), MS/FAB 894.30 again, and calculated value is 894.32。
The synthesis of compound 54
By intermediate e (17.7g, 41mmol), 2- (4- bromophenyls) -4,6- diphenyl -1,3,5- triazines (23.80g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123m Mol dichloromethane after vacuum distillation is extracted with ethyl acetate in return stirring after) being sequentially added into toluene (250mL) Pillar, which is crossed, with hexane obtains compound 54-1 (22.5,7g, 83%).
By compound 54-1 (20.40g, 30.75mmol), 2- (4- bromophenyls) -4,6- diphenyl -1,3,5- triazines (17.86g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) is added to toluene (200mL) return stirring one day later.It is extracted with ethyl acetate two after being evaporated under reduced pressure Chloromethanes/hexane crosses pillar and is recrystallized to give compound 54 (24.13g, 75%), MS/FAB 1046.35, calculated value again It is 1046.38.
The synthesis of compound 56
By the bromo- 4- phenylquinazolines (17.47g, 61.5mmol) of intermediate e (17.7g, 41mmol), 2-, cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) are sequentially added into toluene Return stirring after in (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical combination later Object 56-1 (21.65g, 83%).
By the bromo- 4- phenylquinazolines (7.19g, 46.13mmol) of compound 56-1 (19.57g, 30.75mmol), 2-, iodine Change cuprous (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) and is added to toluene Return stirring one day later (200mL), is extracted with ethyl acetate dichloromethane/hexane after vacuum distillation and crosses pillar and recrystallize again Obtain compound 56 (19.38g, 75%), MS/FAB 840.25, calculated value 840.30.
The synthesis of compound 57
By intermediate e (17.7g, 41mmol), 4- ([1,1'- biphenyl] -4- bases) -2- bromophenyls quinazoline (22.14g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123m Mol return stirring after) being sequentially added into toluene (250mL).Vacuum distillation dichloromethane later is extracted with ethyl acetate Pillar, which is crossed, with hexane obtains compound 57-1 (24.24g, 83%).
By compound 57-1 (21.90g, 30.75mmol), 4- ([1,1'- biphenyl] -4- bases) -2- bromophenyl quinazolines (16.61g, 46.13mmol), cuprous iodide (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) is added to toluene (200mL) return stirring one day later.It is extracted with ethyl acetate two after being evaporated under reduced pressure Chloromethanes/hexane crosses pillar and is recrystallized to give compound 57 (22.89g, 75%), MS/FAB 992.39, calculated value again It is 992.36.
The synthesis of compound 60
By intermediate e (17.7g, 41mmol), the bromo- 4- of 2- (4- butyl benzenes) -6- phenyl -1,3,5- triazines (22.58g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123m Mol return stirring after) being sequentially added into toluene (250mL).Vacuum distillation dichloromethane later is extracted with ethyl acetate Pillar, which is crossed, with hexane obtains compound 60-1 (24.48g, 83%).
The bromo- 4- amylbenzenes (10.43g, 46.13mmol) of compound 60-1 (22.12g, 30.75mmol), 1-, iodate is sub- Copper (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene Return stirring one day later (200mL).Dichloromethane/hexane is crossed pillar and is recrystallized again after vacuum distillation is extracted with ethyl acetate Obtain compound 60 (19.96g, 75%), MS/FAB 865.37, calculated value 865.41.
The synthesis of compound 61
By intermediate e (17.7g, 41mmol), bis- (4- the propyl benzene) -1,3,5- triazines of 2- (3- bromobenzenes) -4,6- (28.97g, 61.5mmol), cuprous iodide (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) Return stirring after being sequentially added into toluene (250mL).It is extracted with ethyl acetate and is evaporated under reduced pressure dichloromethane later and oneself Alkane crosses pillar and obtains compound 61-1 (28.02g, 83%).
The bromo- 4- hexyl benzenes (11.07g, 46.13mmol) of compound 61-1 (25.32g, 30.75mmol), 1-, iodate is sub- Copper (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene Return stirring one day later (200mL).Dichloromethane/hexane is crossed pillar and is recrystallized again after vacuum distillation is extracted with ethyl acetate Obtain compound 61 (22.68g, 75%), MS/FAB 983.52, calculated value 983.49.
The synthesis of compound 62
By intermediate e (17.7g, 41mmol), the bromo- 4- of 2- (4- hexyls phenyl) quinazoline (22.64g, 61.5mmol), iodine Change cuprous (3.9g, 20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol) to be sequentially added into Return stirring after in toluene (250mL).Vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane are crossed pillar and are obtained later Compound 62-1 (24.51g, 83%).
The bromo- 4- heptyl benzenes (11.72g, 46.13mmol) of compound 62-1 (22.15g, 30.75mmol), 1-, iodate is sub- Copper (2.9g, 15.4mmol), ethylenediamine (1.1mL, 20.5mmol) and cesium carbonate (30g, 92.3mmol) are added to toluene Return stirring one day later (200mL).Dichloromethane/hexane is crossed pillar and is recrystallized again after vacuum distillation is extracted with ethyl acetate Obtain compound 62 (20.63g, 75%), MS/FAB 894.50, calculated value 894.47.
With reference to the synthetic method of above compound, other compounds are synthesized, will not enumerate here.
The preparation of organic electroluminescence device is evaluated
[embodiment 1] green organic electrofluorescence device (phosphorescence host)
First, 60nm (N1, N1'- ([1,1'-biphenyl] -4,4'-diyl) bis are deposited in ITO layer (anode) above (N1- (naphthalen-1-yl)-N4, N4-diphenylbenzene-1,4-diamine) forms hole injection layer.Above-mentioned sky N, the change of N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines (NPD) 60nm, the present invention is deposited in cave implanted layer Close object 1 and doping Ir (ppy)3[three (2- phenylpyridines) close iridium] 95:30nm, bis- (2- methyl -8- hydroxyl quinolines is deposited in 5 weight ratios Quinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyls) aluminium (BAlq) hole blocking layer vapor deposition 10nm, vapor deposition electron transfer layer 8- hydroxyl quinolines Quinoline aluminium (Alq3) 40nm, vapor deposition LiF 0.2nm form electron injecting layer, evaporating Al 150nm forms cathode.
[embodiment 2]-[embodiment 42] green organic electrofluorescence device
Other than the compound alternative compounds 1 that the green light material of main part table 1 of luminescent layer is recorded, in accordance with the above-mentioned embodiment 1 together The method of sample prepares organic electroluminescence device.
[comparative example 1]-[comparative example 4]
The comparison compound 1- that the main substance table 1 of luminescent layer is recorded compares an alternate embodiment chemical combination in compound 4 Other than object 1, organic electroluminescence device is obtained according to above-described embodiment same method.
From in above-mentioned table 1 it is found that compound provided by the invention prepare organic electroluminescence device in exciton (exciton) probability that the later doping body of doping body re-moves main body can be moved to significantly reduce, and then increase device Luminous efficiency.Compound provided by the invention has the deep highest track of the energy level for occupying electronics (HOMO) and increases Hole covering (capping) ability, effective configure in luminescent layer occur in electronic equalizing and reduction luminescent layer in luminescent layer Excessive polarization subnumber improve efficiency and service life.
Compound provided by the invention has the deep highest track of energy level (HOMO) and energy gap is bigger, thus hole is justified To luminescent layer, exciton does not fetter and the leakage effect that prevents from shining sliding transporting holes transport layer in luminescent layer, thus increases hair The means reduction of electronic equalizing, the excessive polarization subnumber of reduction, the raisings such as luminescent substance colour purity, service life, efficiency in photosphere.
It is above-mentioned to show to replace which sub-stituent that cause energy gap by sub-stituent type change efficiency and service life, which position (band gap) and characteristic electron, interfacial characteristics vary widely.
Especially, phosphorescence host situation holds the correlation of hole transmission layer and doping, if using similar centerbody It is difficult to the outstanding characteristic electron that compound more provided by the invention than reasoning is shown in phosphorescence host.
[embodiment 43] feux rouges electronic light emitting devices (phosphorescence host)
First, the ITO layer (anode) formed on glass substrate is deposited 2-TNATA 60nm thickness and forms hole injection above Layer, vapor deposition hole transmission layer NPD 60nm on hole injection layer.The compound 31 of material of main part table 2 is deposited above hole transmission layer With dopant (piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iri dium(III) acetylacetonate]/95:5 weight ratio 30nm thickness, vapor deposition hole blocking layer BAlq 10n m thickness, vapor deposition electron-transport Layer Alq340nm thickness, vapor deposition electron injecting layer LiF 0.2nm thickness, evaporating Al 150nm thickness form cathode.
[embodiment 44]~[embodiment 59] glow organic electroluminescent device
Other than the main substance compound 31 for the luminescent layer that compound substitutes in the table 2 of the embodiment of the present invention, according to upper It states 43 same method of embodiment and obtains organic electroluminescence device.
[comparative example 5]~[comparative example 9]
The main substance of luminescent layer substitutes use from the embodiment of the present invention compound 31 and compares compound 1~compare chemical combination In object 6 (compare compound 4 except) other than one, organic electroluminescence device is prepared according to 43 same method of above-described embodiment.
The organic electroluminescence device that above-described embodiment 43~59 and 5~comparative example of comparative example, 9 method manufacture is added into forward direction The bias direct current pressure electroluminescent of PR-650 measuring apparatus (EL) characteristic of Photo Research, brightness 2500cd/m2Base The life test equipment of Zhun Wei cores section (Microchip Technolo gy) company manufacture measures service life T95.Measurement result refers to Table 2.
Table 2
From above-mentioned table 2 it is found that compound use provided by the invention is in feux rouges phosphorescence, the effect of the device prepared Rate and service life also improve very much.In compound provided by the invention, by its inherent characteristic, i.e.,：The deep highest track of energy level (HOMO) energy level effectively adjusts in hole transmission layer to luminescent layer hole and measures, thus hole and is electronically formed in luminescent layer Electronic equalizing and the bed boundary that shines prevent showing tremendous enthusiasm and reach and reduce excessive polaron purpose.Compound provided by the invention uses The service life of organic electroluminescence device obviously increases when material of main part.
In the case of phosphorescence host, the correlation between hole transmission layer and doping is understood, if very using similar main body Difficulty guesses the performance that compound provided by the invention is shown in phosphorescence host.
The present invention does not have the preparation method of the organic electroluminescence device special limitation, using people in the art The preparation method of luminescent device known to member is prepared.In the present invention, film vapor deposition, electron beam can be utilized to steam The methods of hair, physical vapour deposition (PVD) evaporation metal, conductive oxide and their alloy on substrate form sun Pole；The preparation method of cathode is consistent with anode preparation method；The cathode surface being prepared be deposited in order hole injection layer, Hole transmission layer, luminescent layer, air barrier and electron transfer layer.In the present invention, hole injection layer, hole transport are prepared The replacement of high molecular material solvent engineering can be used during the multilayered structures such as layer, luminescent layer, hole blocking layer and electron transfer layer Spin-coating (spin-coating), strip molding (tape-casting), scraping blade method (doctor-blading), silk-screen printing (Screen-Printing), the evaporation coating methods such as ink jet printing or thermal imaging (Thermal-Imaging) reduce the preparation of the number of plies.
Organic electroluminescence device provided by the invention is prepared into using electroluminescent organic material shown in formula 1 It arrives.This organic electroluminescence device has preferable luminescent properties, can front shine, back side illuminated or lighting at two sides.
In the present invention, the organic electroluminescence device is preferred for organic photovoltaic cell (OSC), e-book (e- Paper), Organophotoreceptor (OPC) or polycrystalline organic thin film.
The raw materials used embodiment of the present invention is commercial goods.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims (10)

1. a kind of electroluminescent organic material, which is characterized in that its chemical structural formula is as follows：
In formula, Ar1For total carbon atom number be 6-27 substituted or unsubstituted phenyl or total carbon atom number be 12-20 substitution or Unsubstituted aromatic heterocyclic radical or the substituted or unsubstituted fused ring aryl that total carbon atom number is 10-25；
Ar2For total carbon atom number be 6-21 substituted or unsubstituted phenyl or the total carbon atom number substitution that is 4-20 or unsubstituted Aromatic heterocyclic radical or total carbon atom number be 10-15 substituted or unsubstituted fused ring aryl；
A is hydrogen or phenyl.
2. electroluminescent organic material according to claim 1, which is characterized in that the Ar1It is 7-26 for total carbon atom number Substituted or unsubstituted phenyl or total carbon atom number be 14-19 substituted or unsubstituted aromatic heterocyclic radical or entire carbon atom Number is the substituted or unsubstituted fused ring aryl of 24-25.
3. electroluminescent organic material according to claim 2, which is characterized in that the Ar1It is 9-21 for total carbon atom number Substituted or unsubstituted phenyl or total carbon atom number be 15-16 substituted or unsubstituted aromatic heterocyclic radical, Ar2For total carbon The substituted or unsubstituted aromatic heterocycle that the substituted or unsubstituted phenyl or total carbon atom number that atomicity is 8-18 are 14-18 Base or the substituted or unsubstituted fused ring aryl that total carbon atom number is 14-15.
4. electroluminescent organic material according to claim 3, which is characterized in that the Ar1It is 12- for total carbon atom number 20 substituted or unsubstituted phenyl, Ar2The substituted or unsubstituted phenyl or entire carbon atom for being 11-16 for total carbon atom number Number is the substituted or unsubstituted aromatic heterocyclic radical of 15-16.
5. electroluminescent organic material according to claim 4, which is characterized in that the Ar1It is 16- for total carbon atom number 18 substituted or unsubstituted phenyl, Ar2The substituted or unsubstituted phenyl for being 12-13 for total carbon atom number.
6. electroluminescent organic material according to claim 1, which is characterized in that under the electroluminescent organic material is Any one in row concrete structure：
7. the preparation method of electroluminescent organic material according to claim 1, which is characterized in that include the following steps：
Compound a is dissolved in tetrahydrofuran, is stirred 1 hour after hexane solvent, n-BuLi is added dropwise under the conditions of -78 DEG C； Trimethylborate is added dropwise again, stirs 2h；Then it is added dropwise after hydrochloric acid neutralization, extracts product with ethyl acetate and water, use dichloromethane Alkane and hexane are recrystallized to give compound b；
After compound b, compound c, tetra-triphenylphosphine palladium and potassium carbonate are dissolved in toluene/EtOH/ distilled water, 90 DEG C add Heat 2 hours；It is ground with methanol after organic layer vacuum distillation, obtained solid is dissolved in silica gel filtering after dichloromethane, with two Chlorohexane grinds to obtain compound d；
After triethyl phosphite and dichloro-benzenes is added in compound d, 150 DEG C are stirred overnight；Reaction is concentrated under reduced pressure after terminating It is extracted with ethyl acetate and concentrates again later, compound e is obtained with column chromatography；
By compound e, contain Ar1Bromide, cuprous iodide, ethylenediamine and the cesium carbonate of substituent group return after being sequentially added into toluene Stream stirring, vacuum distillation is extracted with ethyl acetate, and dichloromethane and hexane cross pillar and obtain chemical compounds I later；
Chemical compounds I contains Ar2After bromide, cuprous iodide, ethylenediamine and the cesium carbonate of substituent group are dissolved in toluene, reflux is stirred It mixes one day, is extracted with ethyl acetate after vacuum distillation, dichloromethane/hexane is crossed pillar and is recrystallized to give again described in chemical formula 1 Electroluminescent organic material；
Synthetic route is as follows：
Wherein, Ar1For total carbon atom number be 6-27 substituted or unsubstituted phenyl or total carbon atom number be 12-20 substitution or Unsubstituted aromatic heterocyclic radical or the substituted or unsubstituted fused ring aryl that total carbon atom number is 10-25；
Ar2For total carbon atom number be 6-21 substituted or unsubstituted phenyl or the total carbon atom number substitution that is 4-20 or unsubstituted Aromatic heterocyclic radical or total carbon atom number be 10-15 substituted or unsubstituted fused ring aryl；
A is hydrogen or phenyl.
8. a kind of organic electroluminescence device, including first electrode, second electrode and it is set to the first electrode and the second electricity Organic layer between pole；It is characterized in that, the organic layer includes electroluminescent organic material shown in chemical formula 1.
9. organic electroluminescence device according to claim 8, which is characterized in that the organic layer further include by I main group, More than one metal or its metal complex in II main group, IV main group, V main group transfer metal, lanthanum and d- transfer elements.
10. according to electroluminescent organic material described in claim 1-6 any one, which is characterized in that the organic electroluminescence hair Luminescent material can be applied to organic photovoltaic cell, Electronic Paper, Organophotoreceptor, organic transistor or ink-jet printing material.
CN201810111723.7A 2017-10-25 2018-02-05 Electroluminescent organic material and preparation method thereof and organic electroluminescence device Withdrawn CN108276325A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108822018A (en) * 2017-05-05 2018-11-16 吉林奥来德光电材料股份有限公司 Electroluminescent organic material and preparation method thereof and organic electroluminescence device
WO2024014932A1 (en) * 2022-07-15 2024-01-18 삼성에스디아이 주식회사 Compound for organic optoelectronic diode, composition for organic optoelectronic diode, organic optoelectronic diode and display device

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CN102597158A (en) * 2009-11-03 2012-07-18 第一毛织株式会社 Compound for an organic photoelectric device, and organic photoelectric device comprising same
CN104271700A (en) * 2012-04-03 2015-01-07 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
CN107698486A (en) * 2017-10-09 2018-02-16 长春海谱润斯科技有限公司 A kind of benzo carbazole organic compound and its organic luminescent device

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Publication number Priority date Publication date Assignee Title
CN102597158A (en) * 2009-11-03 2012-07-18 第一毛织株式会社 Compound for an organic photoelectric device, and organic photoelectric device comprising same
CN104271700A (en) * 2012-04-03 2015-01-07 罗门哈斯电子材料韩国有限公司 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
CN107698486A (en) * 2017-10-09 2018-02-16 长春海谱润斯科技有限公司 A kind of benzo carbazole organic compound and its organic luminescent device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108822018A (en) * 2017-05-05 2018-11-16 吉林奥来德光电材料股份有限公司 Electroluminescent organic material and preparation method thereof and organic electroluminescence device
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