CN101445422A - Organic electroluminescent material and application thereof - Google Patents

Organic electroluminescent material and application thereof Download PDF

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CN101445422A
CN101445422A CNA2008102468345A CN200810246834A CN101445422A CN 101445422 A CN101445422 A CN 101445422A CN A2008102468345 A CNA2008102468345 A CN A2008102468345A CN 200810246834 A CN200810246834 A CN 200810246834A CN 101445422 A CN101445422 A CN 101445422A
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dimethyl
methyl
naphthylidene
inferior
naphthacenyl
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CN101445422B (en
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邱勇
李建仁
李银奎
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Abstract

The invention relates to a 1, 2-benzo (a) anthracene derivative and an organic electroluminescent device including the 1, 2-benzo (a) anthracene derivative. The structural general formula of the 1, 2-benzo (a) anthracene derivative is shown on the right, wherein, X and Y are respectively selected from substituted or unsubstituted cyclized arylene group with 4 to 20 carbon nuclear atoms independently. A1 and A2 are respectively selected from substituted or unsubstituted ethylene, substituted or unsubstituted aryl amine group and substituted or unsubstituted carbazyl with 2 to 50 carbon nuclear atoms independently. A1 and A2 can also be hydrogen atoms respectively and independently, but both cannot be hydrogen at the same time. The electroluminescent device made of the 1, 2-benzo (a) anthracene derivative has the advantages of low driving voltage, high luminous efficiency, etc.

Description

A kind of electroluminescent organic material and application thereof
Technical field
The present invention relates to a kind of novel organic compound, belong to field of photovoltaic materials.
Background technology
Organic electroluminescent (hereinafter to be referred as OLED) and corresponding research just began as far back as the sixties in 20th century.People such as p.pope in 1963 have at first found the electro optical phenomenon of organism monocrystalline anthracene, but because the restriction of technical qualification, its driving voltage is failed to cause widely and is paid close attention to up to 400V.The human evaporating Al q such as C.W.Tang of Kodak in 1987 3And HTM-2 made a kind of amorphous membranous type device, and driving voltage has been dropped in the 20V, and OLED just causes common people's concern (US4356429).This class device is owing to have the brightness height, the visual angle is wide, photoelectric response speed is fast, and voltage is low, and power consumption is little, rich color, the contrast gradient height, structure is frivolous, simple technological process and other advantages, can be widely used in planar light-emitting element such as flat-panel monitor and area source, therefore obtain studying widely, develop and used.
As sending out material, the huge legendary turtle compound closes aluminium, coumarin derivatives, tetraphenylbutadiene derivative, diphenylethyllene arylene derivatives with the oxadiazole derivative is known as three (8-hydroxyquinoline roots).It is reported and use these materials can obtain the light of blue light to the ruddiness visual range, and the device that expectation can be developed the display color image (for example, Japanese Patent Application Publication puts down 8 (1996)-239655, flat 7 (1995)-138561 peace 3 (1991)-200289).
Japanese Patent Application Publication flat 8 (1996)-012600 discloses and has adopted the blue-light device of phenylanthracene derivative as luminescent material, but the life-span needs to improve.Be disclosed material (Japanese Patent Application Publication 2001-257074) as the coloured light that turns blue of device at the compound of 9 of anthracene-and 10-have fluoranthene base, its device equally also needs to improve the life-span.Disclose various anthracene derivant in the Japanese Patent Application Publication 2000-182776, do not obtained but these derivatives are in fact synthetic, thereby also just can't make an appraisal these compounds as luminescent material as hole mobile material.U.S. Patent Application Publication (US20070087223) discloses a kind of material dibenzo [a, c] anthracene derivant that is used for the blue light-emitting of organic EL device, device drive voltage, luminous efficiency and all also imperfect to the life-span.International patent application open (WO2007123254) discloses another kind of dibenzo [a, the c] anthracene derivant that is used for organic EL device, but this patent there is no the evaluating data of device aspect, so also can't make an appraisal to these compounds as luminescent material.Japanese Patent Application Publication flat 12 (2000) one 178548 discloses a kind of luminescent material 1 with high heat resistance energy, 2-benzo [a] anthracene derivant, but this material only limits to only contain the aromatic base replacement 1 of C-H, the aromatic base that only contains C-H that 2-benzo [a] anthracene derivant or alcoxyl replace replaces 1,2-benzo [a] anthracene derivant, and the data that do not have the luminescent device aspect equally also just can't be made an appraisal to these compound light-emitting performances as luminescent material equally.
Summary of the invention
Finished the present invention in order to overcome the problems referred to above, and the purpose of this invention is to provide the novel material of a class with high-luminous-efficiency and good carrier transmission performance.
For achieving the above object, the inventor furthers investigate, and found that, has to contain 1 of ad hoc structure shown in the following general formula (1), the compound of 2-benzo [a] anthracene derivant possesses luminescent properties and transmission performance preferably, just is being based on this discovery and has finished the present invention.
The invention provides a kind of 1,2-benzo [a] anthracene derivant shown in following general formula (1):
Figure A200810246834D00301
In the general formula (1), X and Y are selected from the cyclization arylene group of 4～20 nucleus carbon atoms or the replacement cyclization arylene group of 4～20 nucleus carbon atoms respectively alone.
This cyclization aromatic base preferentially is selected from following group: phenylene, 2-methylphenylene, 2,3-dimethyl phenylene, 2,5-dimethyl phenylene, 2,6-dimethyl phenylene, naphthylidene, 2-methyl naphthylidene, 3-methyl naphthylidene, 5-methyl naphthylidene, 6-methyl naphthylidene, 1,3-dimethyl naphthylidene, 1,4-dimethyl naphthylidene, 1,5-dimethyl naphthylidene, 1,6-dimethyl naphthylidene, 1,7-dimethyl naphthylidene, 2,3-dimethyl naphthylidene, 2,4-dimethyl naphthylidene, 2,5-dimethyl naphthylidene, 2,6-dimethyl naphthylidene, 2,7-dimethyl naphthylidene, anthrylene, the methyl anthrylene, dimethyl anthrylene, trimethylammonium anthrylene, the tetramethyl-anthrylene, inferior fluoranthene base, the inferior fluoranthene base of methyl, the inferior fluoranthene base of dimethyl, the inferior fluoranthene base of trimethylammonium, the inferior fluoranthene base of tetramethyl-, phenanthrylene, methyl phenanthrylene, the dimethyl phenanthrylene, the trimethylammonium phenanthrylene, tetramethyl-phenanthrylene, inferior naphthacenyl, inferior naphthacenyl, the inferior naphthacenyl of methyl, the inferior naphthacenyl of dimethyl, inferior pyrenyl, the inferior pyrenyl of methyl, the inferior pyrenyl of dimethyl, the inferior pyrenyl of trimethylammonium, the inferior pyrenyl of tetramethyl-;
A in the general formula (1) 1, A 2Be selected from hydrogen atom respectively alone, or independently be selected from the replacement of 2～50 nucleus carbon atoms or unsubstituted vinyl, replacement or unsubstituted aryl amine, replacement or unsubstituted carbazyl and be not selected from hydrogen atom simultaneously.A in the general formula (1) 1, A 2Preferentially be selected from the group shown in the following general formula:
Figure A200810246834D00311
Above-mentioned A 1And A 2R in the general formula 1～R 5Represent hydrogen atom, have 1～20 nucleus carbon atom number alkane, have the aromatic base that 1～20 nucleus carbon atom is counted the alcoxyl hydrocarbon or had 6～20 nucleus carbon atom numbers.R wherein 4And R 5Can be bonded to ring, perhaps R mutually 4Or R 5Be bonded to ring with X or Y respectively.
R 1～R 3The example of representative comprises hydrogen atom, fluorine atom, bromine atoms, iodine atom, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, basic just, n-heptyl, n-octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methyl cyclohexyl, methoxyl group, oxyethyl group, phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, to tert-butyl-phenyl, p-methoxyphenyl, xenyl, 1-naphthyl, 2-naphthyl, 4-methyl-1-naphthyl, 3-methyl-2-naphthyl, 4-methyl-1-anthryl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl ,-naphthacenyl, 9-naphthacenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl.
In these groups, R 1～R 3Preferably replace or unsubstituted aryl with 6～15 or more a plurality of nucleus carbon atoms, such as phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl is to tert-butyl-phenyl, p-methoxyphenyl, xenyl, 1-naphthyl, 2-naphthyl, 4-methyl-1-naphthyl, 3-methyl-2-naphthyl, 4-methyl-1-anthryl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, with alkyl with 1～20 nucleus carbon atom or alkoxyl group, for example (,) methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, and hydrogen atom, but R 1～R 3Have at least one not to be hydrogen atom.
R 4, R 5The example of representative comprises methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, basic just, n-heptyl, n-octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methyl cyclohexyl, methoxyl group, oxyethyl group, phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, to tert-butyl-phenyl, p-methoxyphenyl, xenyl, 1-naphthyl, 2-naphthyl, 4-methyl-1-naphthyl, 3-methyl-2-naphthyl, 4-methyl-1-anthryl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl ,-naphthacenyl, 9-naphthacenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, wherein R 4～R 5Can be bonded to ring.
In these groups, R 4～R 5Preferably replace or unsubstituted aryl with 6～15 or more a plurality of nucleus carbon atoms, such as phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl is to tert-butyl-phenyl, p-methoxyphenyl, xenyl, 1-naphthyl, 2-naphthyl, 4-methyl-1-naphthyl, 3-methyl-2-naphthyl, 4-methyl-1-anthryl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl and have the alkyl of 1～20 nucleus carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.R wherein 4～R 5Can be bonded to ring mutually, can be bonded to ring with X and Y respectively.
For clearer narration content of the present invention, shown in the general formula of the present invention (1) 1, the preferred embodiment structure of 2-benzo [a] anthracene derivant is as shown in hereinafter, but 1,2-benzo [a] anthracene derivant shown in the general formula (1) is not limited to the shown compound of these preferred embodiments.Following various in, the Me represent methylidene.
Figure A200810246834D00321
Figure A200810246834D00331
Figure A200810246834D00341
Figure A200810246834D00351
Figure A200810246834D00361
Figure A200810246834D00371
Figure A200810246834D00381
Figure A200810246834D00391
Figure A200810246834D00401
Figure A200810246834D00411
Figure A200810246834D00431
Figure A200810246834D00441
Figure A200810246834D00461
Figure A200810246834D00471
Figure A200810246834D00491
Figure A200810246834D00501
Figure A200810246834D00511
Figure A200810246834D00521
Figure A200810246834D00531
Figure A200810246834D00541
Figure A200810246834D00551
Figure A200810246834D00561
Figure A200810246834D00571
This class benzanthrene derivative molecular among the present invention, be a class brand-new can be used for electroluminescent material in the organic EL device.This material can be as electron transport material and the hole mobile material in the organic EL device.This material can also be as being used for organic EL device luminescent layer material of main part or as adulterated dyestuff in the luminescent layer.
Material of the present invention has the following advantages:
Electroluminescent organic material of the present invention can preferentially be used as transport material, comprises as electron transport material and hole mobile material.Simultaneously also can be used as twinkler, comprise separately, perhaps as adulterated dyestuff and luminous as luminescent layer.
Utilize the organic EL device of electroluminescent material preparation of the present invention can show high-performances such as high brightness, high-level efficiency and low driving voltage.
Description of drawings
Fig. 1: brightness-voltage curve of device OLED-1～OLED-6
Fig. 2: the efficient of device OLED-1～OLED-6-current density graphic representation
Fig. 3: current density-voltage curve of device OLED-1～OLED-6
Embodiment
With reference to the following examples the present invention is described more specifically.But the present invention is not limited to these embodiment.
Be the synthetic embodiment of compound of the present invention below:
Except that specifying, most raw material, intermediate used among the present invention are the commercial goods.
The preparation of naphthalene bromide derivative:
Reaction formula:
Figure A200810246834D00581
Experimental detail:
6-bromo-2-naphthalene methyl alcohol (M1) synthetic: under the nitrogen protection, with Lithium Aluminium Hydride (40g, 1.05mol), dry tetrahydrofuran (500mL) joins in the there-necked flask of 5L and form suspension liquid.(141g 0.534mol) is dissolved in 1200mL exsiccant tetrahydrofuran (THF), under the ice bath cooling, slowly is added drop-wise in the there-necked flask by this solution of constant pressure funnel with 6-bromo-2-2-methyl naphthoate in addition.After dripping, continued under cooling conditions stirring reaction 2 hours.Under the cryostat, careful toward the interior methyl alcohol (150mL) that drips of there-necked flask.After adding, continue to stir half an hour.Regulate acidity (about PH=4) with concentrated hydrochloric acid, filtration under diminished pressure is removed insolubles.Filtrate concentrates, it is poured in the water (2L), and the solid that suction filtration is separated out, washing, small amount of ethanol is washed, and vacuum-drying gets 6-bromo-2-naphthalene methyl alcohol (95.4g).
6-bromo-2-brooethyl naphthalene (M2) synthetic: with 6-bromo-2-naphthalene methyl alcohol (47.7g, 0.201mol), chloroform (600mL) joins in the there-necked flask of 2L and form suspension liquid.Ethanol-liquid nitrogen bath is cooled to about-35 ℃, and (28.6ml 0.603mol), dripped off in about 25 minutes slowly to drip phosphorus tribromide.Remove cryostat, at room temperature continued stirring reaction 2.5 hours.Under the ice bath, slowly drip methyl alcohol (250mL), acutely emit bromize hydrogen gas, make tail gas with potassium hydroxide solution and absorb.The solid that filtration under diminished pressure is separated out, ethanol drip washing filter cake, oven dry gets white solid 6-bromo-2-brooethyl naphthalene (35g).
6-bromo-2-naphthyl methylene dimethylphosphite (M3) synthetic: with 6-bromo-2-brooethyl naphthalene (35.0g, 0.117mol) and trimethyl phosphite (18mL 0.152mol) joins in the there-necked flask (250ml) and was heated to 150 ℃ of back flow reaction 3 hours.Decompression steams unnecessary trimethyl phosphite, cools off, and separates out white solid, and crushing with petroleum ether, is filtered, and is empty really dry, gets white solid 6-bromo-2-naphthyl methylene dimethylphosphite (43g).
6-bromo-2-naphthaldehyde (M4) synthetic: under the nitrogen protection, with 6-bromo-2-naphthalene methyl alcohol (40.0g, 0.170mol) and methylene dichloride (1.6L) join in the there-necked flask (2L) the formation clear solution.Under the magnetic agitation, and disposable adding pyridinium chlorochromate drone salt (40.0g, 0.186mol), the rapid blackening of reaction solution.Continue stirring reaction after 1 hour, reaction mixture is crossed quick silicagel column, with eluent methylene chloride, filtrate is filtered with anhydrous magnesium sulfate drying, the rotation solvent evaporated, the gained solid obtains white solid 6-bromo-2-naphthaldehyde (31g) with 50% aqueous ethanolic solution recrystallization.
Synthesizing of embodiment one compd E 19:
Synthetic route:
Figure A200810246834D00591
Experimental detail:
Intermediate M5's is synthetic: the same M3 of method, just change raw material 6-bromo-2-brooethyl naphthalene into 4-methyl bromobenzyl, and get M5 (yield 98%).
Intermediate M6's is synthetic: in being furnished with the 100ml there-necked flask of nitrogen protection device, whipping appts, reflux condensate device, add M4 (4.70 grams, 0.020mol), M5 (4.71 grams; 0.022mol), sodium hydride (1.28 grams, 0.030mol), absolute anhydrous tetrahydro furan 25ml, stir about is 12 hours under the reflux state; cooling; slowly drip methyl alcohol 2ml, reactant is poured in the 50ml water, filter the solid of separating out; dry; with re-crystallizing in ethyl acetate, get M6 (5.49 grams, yield is 85%).
Compd E 19 synthetic: in being furnished with the 500ml there-necked flask of nitrogen protection device, whipping appts, reflux condensate device, add M6 (4.52 grams, 14mmol) and THF60ml.Dropping n-BuLi under-78 ℃ (2.9M, 4.8ml, 14mmol), insulated and stirred 30min.(1.55 restrain, 6.0mmol) to add 1,2-benzo [a] anthraquinone then.After adding, be warming up to room temperature naturally.Add 50ml water, ethyl acetate extraction (50ml*3), rotation boils off solvent, adds the 50ml glacial acetic acid in the interior residue of bottle, KI (4.15 grams, 25mmol) and inferior sodium phosphate (7.62 restrain, 72mmol), heating reflux reaction 1 hour, the product of separating out is filtered in cooling.Use acetate successively, ethanol and water washing filter cake, vacuum-drying gets faint yellow solid 5.57g.
Product MS (m/e): 712, corresponding to: C 56H 40=712, prove that this chemical combination is E19 (yield: 92%).
Synthesizing of embodiment two compd Es 32:
Synthetic route:
Figure A200810246834D00601
Experimental detail:
Intermediate M7's is synthetic: the same M3 of method, just change raw material 6-bromo-2-brooethyl naphthalene into the phenylbenzene monobromethane, and get M7 (yield 90%).
Intermediate M8's is synthetic: under the argon shield; in the 250mL there-necked flask, add 1; 4-dibromine naphthalene (5.72g, 0.020mol), Tetramethyl Ethylene Diamine (5.3ml, 0.040mol) and dry tetrahydrofuran (60mL); stir; ethanol-liquid nitrogen bath is cooled to-78 ℃, slowly drips n-BuLi (2.5M, 8ml; 0.020mol), get dark blue solution.Finish, insulated and stirred 1 hour, (DMF, 15.1ml 0.2mol) are dissolved in the solution of THF (15ml) slowly to drip dimethyl sulfoxide (DMSO).Remove cryostat, rise to room temperature, 10% hydrochloric acid (55mL) of dropping, stirring reaction 1 hour.Separatory, the ethyl acetate extraction water merges organicly, and anhydrous magnesium sulfate drying filters, and rotation boils off solvent, and the gained solid obtains light yellow solid M8 (2.58 grams, yield 55%) with ethanol-ethyl acetate (V/V=2:1) recrystallization.
Intermediate M9's is synthetic: the same M6 of method, just change M3 and M5 into M8 and M7 respectively, and get yellow crystals M9 (yield 85%).
Synthesizing of compd E 32: the same E19 of method, just change M6 into M9, get orange/yellow solid 0.9 gram.
Product MS (m/e): 837, corresponding to: C 66H 44=837, prove that this chemical combination is E32 (yield: 78%).
Synthesizing of embodiment three compd Es 33:
Synthetic route:
Figure A200810246834D00611
Experimental detail:
Intermediate M10's is synthetic: the same M9 of method, just change M8 into M4, and get pale yellow solid M10 (yield 83%).
Synthesizing of compd E 33: the same E19 of method, just change M6 into M10, get orange/yellow solid 1.6 grams.
Product MS (m/e): 837, corresponding to: C 66H 44=837, prove that this chemical combination is E33 (yield: 83%).
Embodiment Four Modernizations compound E68's is synthetic:
Reaction formula:
Figure A200810246834D00621
Experimental detail:
Intermediate M11's is synthetic: the same E19 of method, just change M6 into paradibromobenzene, and get pale yellow solid M11 (yield 83%).
Synthesizing of compd E 68: under the argon shield; in the 50mL there-necked flask, add M11 (1.08g; 2mmol), sodium tert-butoxide (1.14g; 12mmol), N-phenyl-2-naphthylamines (0.96g; 4.4mmol), palladium (0.04g; 0.2mmol), (0.10g, 0.4mmol) and dry toluene 25mL, magnetic agitation refluxes and spends the night triphenyl phosphorus.Short column is crossed in cooling, elimination black thick substances, and toluene drip washing, filtrate being spin-dried for obtains the tawny thick substances, cooling curing, porphyrize refluxes with dehydrated alcohol, and hot suction filtration obtains yellow powder 1.4 grams.
Product MS (m/e): 815, corresponding to: C 62H 42N 2=815, prove that this chemical combination is E68 (yield: 86%).
Synthesizing of embodiment five compd Es 108:
Reaction formula:
Figure A200810246834D00631
Experimental detail:
The same E19 of method just changes M6 into 3-bromine-N-ethyl carbazole, gets yellow solid 2.5 grams.
Product MS (m/e): 615, corresponding to: C 46H 34N 2=615, prove that this chemical combination is E68 (yield: 93%).
Synthesizing of embodiment six compd Es 122:
Reaction formula:
Experimental detail:
In the 100ml there-necked flask of nitrogen protection; add M11 (1.08g; 2mmol), 4-pyridine boric acid (0.64g; 5.2mmol), Palladous chloride (0.07g; 0.4mmol), triphenylphosphine (0.21g; 0.8mmol), Anhydrous potassium carbonate (3.31g, 24mmol), toluene 35ml, ethanol 23ml, water 32ml, magnetic agitation heating reflux reaction 8h.Cooling, separatory, rotation boils off solvent, and column chromatography for separation is purified, and the sherwood oil wash-out is used 1/10 ethyl acetate+sherwood oil (v/v) wash-out again, gets light yellow solid 1.02 grams.
Product MS (m/e): 534, corresponding to: C 40H 26N 2=534, prove that this chemical combination is E122 (yield: 96%).
Synthesizing of embodiment seven compd Es 153:
Reaction formula:
Figure A200810246834D00641
Experimental detail:
Intermediate M12's is synthetic: the same E19 of method, just change M6 into bromo-iodobenzene, and get yellow solid M12 (yield 87%).
Synthesizing of compd E 153: the same E122 of method, just change 4-pyridine boric acid into 3-pyridine boric acid, obtain yellow powder 1.25 grams.
Product MS (m/e): 534, corresponding to: C 40H 26N 2=534, prove that this chemical combination is E153 (yield: 85%).
Synthesizing of embodiment eight compd Es 154:
Reaction formula:
Figure A200810246834D00642
Experimental detail:
The same E153 of method just changes 3-pyridine boric acid into 3-quinoline boric acid, obtains yellow powder 1.6 grams.
Product MS (m/e): 634, corresponding to: C 48H 30N 2=634, prove that this chemical combination is E154 (yield: 91%).
Synthesizing of embodiment nine compd Es 163:
Reaction formula:
Figure A200810246834D00651
Intermediate M13's is synthetic: the same E19 of method, just change M6 into equal tribromo-benzene, and get yellow solid M13 (yield 82%).
Synthesizing of compd E 163: the same E153 of method obtains yellow powder 1.88 grams.
Product MS (m/e): 688, corresponding to: C 50H 32N 4=688, prove that this chemical combination is E163 (yield: 78%).
Synthesizing of embodiment ten compd Es 186:
Reaction formula:
Intermediate M14's is synthetic: in the 100ml single port bottle, add 1,2-benzo [a] anthracene (3.42g, 15mmol), the N-bromo-succinimide (NBS, 3.56g, 20mmol) and 65ml DMF, stirring reaction under the room temperature, TLC monitors reaction end, and reaction finishes, and good the stirring slowly drips water down, add and continue to stir 30min again, the solid that suction filtration is separated out, the dehydrated alcohol recrystallization gets yellow solid M14 (yield 70%).
Intermediate M15's is synthetic: the same E122 of method, just change 4-pyridine boric acid into N, N-two (4,4 '-xylyl) to phenylo boric acid, get yellow solid M15 (yield 60%).
Intermediate M16's is synthetic: in the 100ml single port bottle, add M15 (1.50g, 3mmol), anhydrous cupric bromide (NBS, 0.69g, 3.1mmol) and the anhydrous chlorobenzene of 80ml, 40 ℃ of following stirring reactions 24 hours, reaction finishes, and by quick silicagel column, rotation boils off solvent, the gained solid gets yellow crystals M16 (yield 70%) with the benzene recrystallization.
Synthesizing of compd E 186: the same M15 of method, just with N, N-two (4,4 '-xylyl) phenylo boric acid is changed into 1,1-diphenylethyllene-2-phenyl-4-boric acid, get orange/yellow solid 1.2 grams.
Product MS (m/e): 754, corresponding to: C 58H 43N=754 proves that this chemical combination is E186 (yield: 58%).
Synthesizing of embodiment 11 compd Es 198:
Reaction formula:
Figure A200810246834D00671
Experimental detail:
Compd E 198 synthetic: the same E186 of method, just with N, N-two (4,4 '-xylyl) changes N into to phenylo boric acid, phenylo boric acid between N-two (4,4 '-xylyl), orange/yellow solid 0.95 gram.
Product MS (m/e): 754, corresponding to: C 58H 43N=754 proves that this chemical combination is E198 (yield: 58%).
Synthesizing of embodiment 12 compd Es 229:
Reaction formula:
Experimental detail:
Intermediate M19's is synthetic: with M12 (8.07g; 15mol); carbazole (2.76g, 16mol); cupric iodide (2.86g, 16mol); Anhydrous potassium carbonate (4.17g; 30mol); 18-is preced with-6 (0.08g; 2mol) and 1,3-DMPU (DMPU) 45ml puts in the 100ml there-necked flask, under the argon shield; reflux 5 hours; be chilled to room temperature, the good stirring slowly drips water down, adds and continues to stir 1h again; the solid that suction filtration is separated out; washing with chloroform dissolving gained solid, is crossed quick post; concentrate; add ethanol, the solid that suction filtration is separated out gets yellow solid 7.96 gram M19 (yields: 85%).
Intermediate M20's is synthetic: the same M8 of method, just change 1,4-dibromine naphthalene into M19, and get yellow solid M20 (yield: 50%).
Synthesizing of compd E 229: the same M9 of method, just change M8 into M20, get orange/yellow solid 1.3 grams.
Product MS (m/e): 724, corresponding to: C 58H 43N=724 proves that this chemical combination is E229 (yield: 88%).
Synthesizing of embodiment 13 compd Es 251:
Reaction formula:
Experimental detail:
The same E68 of method, just N-phenyl-2-naphthylamines and M11 are changed into 4,4 respectively '-dimethyl pentanoic and M19, orange/yellow solid 1.7 grams.
Product MS (m/e): 740, corresponding to: C 58H 43N=740 proves that this chemical combination is E251 (yield: 90%).
Be the Application Example of The compounds of this invention below:
The preferred implementation of fabricate devices:
The typical structure of OLED device is:
Substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode
Substrate can use the substrate in traditional organic luminescent device, for example: glass or plastics.Anode material can adopt transparent high conductivity material, indium tin oxygen (ITO) for example, indium zinc oxygen (IZO), tindioxide (SnO2), zinc oxide (ZnO) etc.Select glass substrate for use in element manufacturing of the present invention, ITO makes anode material.
Hole transmission layer can adopt N, N '-two (3-tolyl)-N, N '-phenylbenzene-[1, the 1-xenyl]-4,4 '-diamines (TPD) or N, N '-phenylbenzene-N, N '-two (1-naphthyl)-(1,1 '-xenyl)-4,4 '-diamines tri-arylamine group materials such as (NPB).Wherein NPB is the hole mobile material of using always, and hole mobile material selected in element manufacturing of the present invention is selected NPB for use.
Device architecture can also can be the multi-luminescent layer structure for the single-shot photosphere; Every layer of luminescent layer can also can be doped structure for single-shot light body luminescent material structure; Luminescent dye can select for use fluorescent material also can select phosphor material for use; Glow color is not limit, can for as red, yellow, blue, green etc.Selected luminescent material is The compounds of this invention E68 in element manufacturing of the present invention.
The electric transmission layer material uses 4 usually, 7-phenylbenzene-1, adjacent phenanthroline (BPhen) of 10-and Alq 3, in element manufacturing of the present invention, use BPhen and Alq simultaneously 3
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., it also can be electron injecting layer/metal-layer structure, as common cathode constructions such as LiF/Al, Li2O, wherein electron injecting layer can be simple substance, compound or the mixture of basic metal, alkaline-earth metal, transition metal, also can be the composite cathode structure that multilayer material constitutes.Selected cathode material is Mg:Ag/Ag in element manufacturing of the present invention.
The different materials of using among the present invention is as follows:
Figure A200810246834D00701
The preparation and the result of embodiment 14 El elements
Preparation OLED-1: sheet glass supersound process in commercial clean-out system that will be coated with the ITO transparency conducting layer, in deionized water, wash, at acetone: ultrasonic oil removing in the alcohol mixed solvent, under clean environment, be baked to and remove moisture content fully, with UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface.
The above-mentioned anodic glass substrate that has is placed in the vacuum chamber, be evacuated to 1 * 10-5～9 * 10-3Pa, vacuum evaporation NPB is as hole transmission layer on above-mentioned anode tunic, and evaporation speed is 0.1nm/s, and the evaporation thickness is 50nm;
Vacuum evaporation one deck NNPA on hole transmission layer, this compound is as luminescent material, and its evaporation speed is 0.1nm/s, and the evaporation total film thickness is 50nm; Simultaneously, evaporation one deck is as the The compounds of this invention E68 of luminescent material on NNPA, and the relative mass that makes NNPA:E68 is 50:2.Formed film is as luminescent layer.
On the luminescent layer of above-mentioned formation, evaporation one deck Alq 3, its evaporation speed is 0.1nm/s, the evaporation total film thickness is 30nm, as electron transfer layer;
On electron transfer layer successively vacuum evaporation Mg:Ag alloy layer and Ag layer as the negative electrode of device, wherein the Mg:Ag alloy layer doping than being 10:1, thickness is 100nm, the evaporation speed of Ag layer is 0.3nm/s, thickness is 50nm.
As stated above, change the mass ratio of NNPA and E68, can make OLED-2～OLED-4 respectively, change E68 into DDPNAV, then can make OLED-5 and OLED-6.
Device performance sees Table 1 and accompanying drawing 1 and accompanying drawing 2 (device architecture: ITO/NPB/ luminescent layer film/Alq 3/ Mg:Ag/Ag, luminescent layer film composition sees the following form):
Table 1
The device sequence number The luminescent layer film Require brightness cd/m 2 Driving voltage V Current density A/m 2 Current efficiency cd/A Luminous efficiency Im/W
OLED—1 NNPA:E68(1％) 5000 6.43 1533.02 3.26 1.59
OLED—2 NNPA:E68(3％) 5000 6.39 778.16 6.43 3.16
OLED—3 NNPA:E68(5％) 5000 6.59 857.72 5.83 2.78
OLED—4 NNPA:E68(7％) 5000 6.79 958.74 5.22 2.41
OLED—5 NNPA:DDPANV(1％) 5000 11.77 3409.16 3.41 0.91
OLED—6 NNPA:DDPANV(3％) 5000 7.37 1970.63 2.54 1.08
As can be seen from Table 1, among the embodiment 14, use organic EL device OLED-1～OLED-4 of The compounds of this invention E68, under the 5000nit high brightness, demonstrated low driving voltage and higher luminous efficiency.By contrast, organic EL device OLED-5 and OLED-6 then present higher driving voltage and lower luminosity factor.
Although describe the present invention in conjunction with the embodiments, but the present invention is not limited to the foregoing description and accompanying drawing, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.

Claims (4)

1, a kind of 1,2-benzo [a] anthracene derivant shown in following general formula (1):
Figure A200810246834C00021
In the general formula (1), X and Y are selected from the cyclization arylene group of 4～20 nucleus carbon atoms or the replacement cyclization arylene group of 4～20 nucleus carbon atoms, A respectively alone 1, A 2Be selected from hydrogen atom respectively alone, or independently be selected from replacement or unsubstituted vinyl, replacement or unsubstituted aryl amine, replacement or the unsubstituted carbazyl of 2～50 nucleus carbon atoms, and be not selected from hydrogen atom simultaneously.
2, according to claim 11,2-benzo [a] anthracene derivant, X in the general formula (1) and Y are selected from phenylene respectively alone, 2-methylphenylene, 2,3-dimethyl phenylene, 2,5-dimethyl phenylene, 2,6-dimethyl phenylene, naphthylidene, 2-methyl naphthylidene, 3-methyl naphthylidene, 5-methyl naphthylidene, 6-methyl naphthylidene, 1,3-dimethyl naphthylidene, 1,4-dimethyl naphthylidene, 1,5-dimethyl naphthylidene, 1,6-dimethyl naphthylidene, 1,7-dimethyl naphthylidene, 2,3-dimethyl naphthylidene, 2,4-dimethyl naphthylidene, 2,5-dimethyl naphthylidene, 2,6-dimethyl naphthylidene, 2,7-dimethyl naphthylidene, anthrylene, the methyl anthrylene, dimethyl anthrylene, trimethylammonium anthrylene, the tetramethyl-anthrylene, inferior fluoranthene base, the inferior fluoranthene base of methyl, the inferior fluoranthene base of dimethyl, the inferior fluoranthene base of trimethylammonium, the inferior fluoranthene base of tetramethyl-, phenanthrylene, methyl phenanthrylene, the dimethyl phenanthrylene, the trimethylammonium phenanthrylene, tetramethyl-phenanthrylene, inferior naphthacenyl, inferior naphthacenyl, the inferior naphthacenyl of methyl, the inferior naphthacenyl of dimethyl, inferior pyrenyl, the inferior pyrenyl of methyl, the inferior pyrenyl of dimethyl, the inferior pyrenyl of trimethylammonium, the inferior pyrenyl of tetramethyl-;
A in the general formula (1) 1, A 2Independently be selected from hydrogen atom respectively or be selected from the group shown in the following general formula, and A 1And A 2Be not selected from hydrogen atom simultaneously:
Figure A200810246834C00031
Above-mentioned R 1～R 5Represent hydrogen atom, have 1～20 nucleus carbon atom number alkane, have the aromatic base that 1～20 nucleus carbon atom is counted the alcoxyl hydrocarbon or had 6～20 nucleus carbon atom numbers.R wherein 4And R 5Can be bonded to ring, perhaps R mutually 4Or R 5Be bonded to ring with X or Y respectively.
3,1,2-benzo according to claim 1 and 2 [a] anthracene derivant, R 1～R 5Be selected from hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, basic just, n-heptyl, n-octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methyl cyclohexyl, methoxyl group, oxyethyl group, phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, to tert-butyl-phenyl, p-methoxyphenyl, xenyl, 1-naphthyl, 2-naphthyl, 4-methyl-1-naphthyl, 3-methyl-2-naphthyl, 4-methyl-1-anthryl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl, 9-naphthacenyl, 1-pyrenyl, 2-pyrenyl or 4-pyrenyl;
R wherein 4And R 5Can be bonded to ring, perhaps R mutually 4Or R 5Be bonded to ring with X or Y respectively.
4,1,2-benzo according to claim 1 and 2 [a] anthracene derivant, the molecular structural formula of preferred material is as follows, Me represent methylidene wherein:
Figure A200810246834C00032
Figure A200810246834C00041
Figure A200810246834C00051
Figure A200810246834C00061
Figure A200810246834C00071
Figure A200810246834C00081
Figure A200810246834C00091
Figure A200810246834C00101
Figure A200810246834C00111
Figure A200810246834C00131
Figure A200810246834C00141
Figure A200810246834C00151
Figure A200810246834C00161
Figure A200810246834C00171
Figure A200810246834C00181
Figure A200810246834C00191
Figure A200810246834C00201
Figure A200810246834C00211
Figure A200810246834C00221
Figure A200810246834C00231
Figure A200810246834C00241
Figure A200810246834C00271
Figure A200810246834C00281
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