CN101987822B - Organic electroluminescent material and application thereof - Google Patents

Organic electroluminescent material and application thereof Download PDF

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CN101987822B
CN101987822B CN200910090379.9A CN200910090379A CN101987822B CN 101987822 B CN101987822 B CN 101987822B CN 200910090379 A CN200910090379 A CN 200910090379A CN 101987822 B CN101987822 B CN 101987822B
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alkane
aromatic group
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CN101987822A (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 containing the compound. The general structural formula of the compound is shown in a structural general formula (1), wherein A1 and A2 are independently selected from aromatic groups with 6 to 25 nuclear carbon atoms respectively, or selected from substituent groups represented by the general formulae (1) to (4). The material of the invention can be preferably used as a luminous body, and simultaneously can be used as a transmission material. The electroluminescent device manufactured by the material of the invention has the high performances of low drive voltage, high luminescent efficiency and the like.

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 electroluminescence device (Organic light-emitting device, hereinafter to be referred as OLED) and corresponding research just started as far back as the sixties in 20th century.First the people such as p.pope in 1963 have found the electro optical phenomenon of Organic Crystals anthracene, but due to the restriction of technical qualification, its driving voltage, up to 400V, is failed to cause widely and paid close attention to.It (is Alq that the people such as C.W.Tang of Kodak in 1987 close aluminium with evaporation three (oxine root) 3) and HTM-2 made a kind of amorphous membranous type device, driving voltage has been dropped in 20V, OLED just causes that common people pay close attention to (US4356429).Brightness is high, visual angle is wide, photoelectric response speed is fast, voltage is low, power consumption is little owing to having for this class device, rich color, contrast gradient is high, structure is frivolous, simple technological process and other advantages, can be widely used in planar light-emitting element as flat-panel monitor and area source, thereby obtain studying widely, develop and used.
As luminescent material, as Alq 3, coumarin derivatives, tetraphenylbutadiene derivative, diphenylethyllene arylene derivatives be with oxadiazole derivative etc. are known.It is reported and use these materials can obtain blue light to the light in ruddiness visual range, and expectation (for example can be developed chromatic display, 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 phenylanthracene derivative as the blue-light device of luminescent material, but the life-span needs to improve.At the 9-of anthracene and 10-, with the compound of fluoranthene base, be disclosed the coloured light material (Japanese Patent Application Publication 2001-257074) that turns blue as device, its device equally also needs to improve the life-span.Various anthracene derivant as hole mobile material is disclosed in Japanese Patent Application Publication 2000-182776, but these derivatives synthetic obtaining in fact, thereby the compounds property that also just cannot be used as luminescent material to these be made an appraisal.U.S. Patent Application Publication (US20070087223) discloses a kind of material dibenzo [a, c] anthracene derivant of the blue light-emitting for organic EL device, the driving voltage of device, luminous efficiency and all not very good to the life-span.International Patent Application Publication (WO2007123254) discloses the another kind of dibenzo [a for organic EL device, c] anthracene derivant, but this patent there is no the evaluating data of device aspect, therefore also cannot make suitable evaluation by the compounds property as luminescent material to these.Japanese Patent Application Publication flat 12 (2000)-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 there is no equally luminescent device aspect, also just cannot the compound light-emitting performance as luminescent material make an appraisal to these equally.In addition, International Patent Application Publication (WO2008145239) has been mentioned 1 of a kind of nitrogen atom, 2-benzo [a] anthracene derivant, 2,4,5 or 6 single secondary amine or N-carbazyl monosubstituted 1 have wherein been related to, 2-benzo [a] anthracene derivant, but in fact 1, it is 7 that 2-benzo [a] anthracene chemistry replaces the most active position, as electronic material, need to carry out function replacement or protection just can better be used; Or be that 7,12 or 6,12 two secondary amine or two (N-carbazyl) two replace 1,2-benzo [a] anthracene derivants, but connect two secondary amine or two (N-carbazyl) at 7,12, because steric hindrance causes implementing difficulty too greatly, too greatly even cannot implement.This patent is not clearly mentioned the derivative that the upper independent secondary amine of 7 of 1,2-benzo [a] anthracenes or N-carbazyl replace, do not have yet above-mentioned 1, the material luminescent properties data that 2-benzo [a] anthracene series derivates is relevant.
Summary of the invention
In order to overcome the problems referred to above, complete the present invention, and the object 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 conducts in-depth research such material, found that, has 1 shown in general formula (1) below, 2-benzo [a] anthracene derivant possesses good luminescent properties and transmission performance, has completed the present invention just based on this discovery.
The invention provides a kind of as shown in following general formula (1) 1,2-benzo [a] anthracene derivant:
Figure G2009100903799D00021
In general formula (1), A 1and A 2be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms, for example some represented groups below:
Figure G2009100903799D00022
Figure G2009100903799D00031
Etc.; Or be selected from below general formula (1-1) to the substituted radical of (1-4) representative:
Figure G2009100903799D00041
Ar wherein 11and Ar 12be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms, as phenyl, 2-aminomethyl phenyl, 4-aminomethyl phenyl, 2, 4-3,5-dimethylphenyl, to tert-butyl-phenyl, 4-xenyl, 3-xenyl, 2-xenyl, terphenyl, tetrad phenyl, 1-naphthyl, 2-naphthyl, 4-methyl isophthalic acid-naphthyl, 3-methyl-2-naphthyl, to (Alpha-Naphthyl) phenyl, to (betanaphthyl) phenyl, between (Alpha-Naphthyl) phenyl, between (betanaphthyl) phenyl, to (Alpha-Naphthyl) xenyl, to (betanaphthyl) xenyl, between (Alpha-Naphthyl) xenyl, between (betanaphthyl) xenyl, 2-anthryl, 9, 10-phenylbenzene-2-anthryl, 9-phenanthryl, 3-fluoranthene base, pyrenyl, perylene base, Deng,
L 1for thering is the arylene group of 6～25 nucleus carbon atoms, as Isosorbide-5-Nitrae-phenylene, 1,3-phenylene, 2,5-dimethyl phenylene, 2,4-dimethyl phenylene, naphthylidene, anthrylene, phenanthrylene, sub-pyrenyl, sub-fluoranthene base, etc.;
R 21and R 22select alone respectively hydrogen atom, alkane or the alcoxyl hydrocarbon with 1～6 nucleus carbon atom, as methyl, ethyl, propyl group, sec.-propyl, isobutyl-, normal-butyl, the tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, methoxyl group, oxyethyl group, etc., or there is the aromatic group of 6～25 nucleus carbon atoms, as phenyl, 2-aminomethyl phenyl, 4-aminomethyl phenyl, 2, 4-3,5-dimethylphenyl, to tert-butyl-phenyl, 4-xenyl, 3-xenyl, 2-xenyl, terphenyl, tetrad phenyl, 1-naphthyl, 2-naphthyl, 4-methyl isophthalic acid-naphthyl, 3-methyl-2-naphthyl, to (Alpha-Naphthyl) phenyl, to (betanaphthyl) phenyl, between (Alpha-Naphthyl) phenyl, between (betanaphthyl) phenyl, to (Alpha-Naphthyl) xenyl, to (betanaphthyl) xenyl, between (Alpha-Naphthyl) xenyl, between (betanaphthyl) xenyl, 2-anthryl, 9, 10-phenylbenzene-2-anthryl, 9-phenanthryl, 3-fluoranthene base, pyrenyl, perylene base, etc.,
L 2for thering is the arylene group of 6～25 nucleus carbon atoms, as Isosorbide-5-Nitrae-phenylene, 1,3-phenylene, 2,5-dimethyl phenylene, 2,4-dimethyl phenylene, naphthylidene, anthrylene, phenanthrylene, sub-pyrenyl, sub-fluoranthene base, etc.;
R 31be selected from respectively the alkane with 1～6 nucleus carbon atom, as methyl, ethyl, propyl group, sec.-propyl, isobutyl-, normal-butyl, the tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.; Or there is the aromatic group of 6～25 nucleus carbon atoms, and as phenyl, 2-aminomethyl phenyl, 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyl, to tert-butyl-phenyl, 4-xenyl, 3-xenyl, 2-xenyl, terphenyl, tetrad phenyl, 1-naphthyl, 2-naphthyl, to (Alpha-Naphthyl) phenyl, to (betanaphthyl) phenyl, (Alpha-Naphthyl) phenyl, between (betanaphthyl) phenyl, to (Alpha-Naphthyl) xenyl, to (betanaphthyl) xenyl, (Alpha-Naphthyl) xenyl, between (betanaphthyl) xenyl, etc.;
R 32be selected from respectively hydrogen atom, alkane or the alcoxyl hydrocarbon with 1～6 nucleus carbon atom, as as methyl, ethyl, propyl group, sec.-propyl, isobutyl-, normal-butyl, the tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, methoxyl group, oxyethyl group, etc., or there is the aromatic group of 6～25 nucleus carbon atoms, as phenyl, 2-aminomethyl phenyl, 4-aminomethyl phenyl, 2, 4-3,5-dimethylphenyl, 4-xenyl, 3-xenyl, 2-xenyl, terphenyl, tetrad phenyl, 1-naphthyl, 2-naphthyl, 4-methyl isophthalic acid-naphthyl, 3-methyl-2-naphthyl, to (Alpha-Naphthyl) phenyl, to (betanaphthyl) phenyl, between (Alpha-Naphthyl) phenyl, between (betanaphthyl) phenyl, to (Alpha-Naphthyl) xenyl, to (betanaphthyl) xenyl, between (Alpha-Naphthyl) xenyl, between (betanaphthyl) xenyl, etc.,
Ar 41～Ar 43be selected from respectively hydrogen atom, there is the alkane of 1～6 nucleus carbon atom or there is the aromatic group of 6～25 nucleus carbon atoms, as phenyl, 2-aminomethyl phenyl, 4-aminomethyl phenyl, 2, 4-3,5-dimethylphenyl, to tert-butyl-phenyl, 4-xenyl, 3-xenyl, 2-xenyl, terphenyl, tetrad phenyl, 1-naphthyl, 2-naphthyl, 4-methyl isophthalic acid-naphthyl, 3-methyl-2-naphthyl, to (Alpha-Naphthyl) phenyl, to (betanaphthyl) phenyl, between (Alpha-Naphthyl) phenyl, between (betanaphthyl) phenyl, to (Alpha-Naphthyl) xenyl, to (betanaphthyl) xenyl, between (Alpha-Naphthyl) xenyl, between (betanaphthyl) xenyl, etc.,
L 3for thering is the arylene group of 6～25 nucleus carbon atoms, as Isosorbide-5-Nitrae-phenylene, 1,3-phenylene, 2,5-dimethyl phenylene, 2,4-dimethyl phenylene, naphthylidene, anthrylene, phenanthrylene, sub-pyrenyl, sub-fluoranthene base, etc.;
In general formula (1), A 1and A 2can be identical, also can be different.
For clearer narration content of the present invention, shown in general formula of the present invention (1) 1, the preferred embodiment structure of 2-benzo [a] anthracene derivant as shown below, but 1 shown in general formula (1), 2-benzo [a] anthracene derivant is not limited to the shown compound of these preferred embodiments.Preferred embodiment structure is:
Figure G2009100903799D00061
Figure G2009100903799D00071
Figure G2009100903799D00081
Figure G2009100903799D00091
Figure G2009100903799D00101
Figure G2009100903799D00111
Figure G2009100903799D00121
Figure G2009100903799D00131
Figure G2009100903799D00141
Figure G2009100903799D00151
Figure G2009100903799D00161
Figure G2009100903799D00171
Figure G2009100903799D00181
Figure G2009100903799D00191
Figure G2009100903799D00201
Figure G2009100903799D00211
Figure G2009100903799D00221
Figure G2009100903799D00231
Figure G2009100903799D00241
Figure G2009100903799D00251
Figure G2009100903799D00261
Figure G2009100903799D00281
Figure G2009100903799D00291
Figure G2009100903799D00301
This class benzanthrene derivative molecular in the present invention, be a class new can be used for the electroluminescent material in organic EL device.This material can be as luminescent layer material of main part in organic EL device or as the dyestuff adulterating in luminescent layer.This material can also be as hole-injecting material and the hole mobile material in organic EL device.
Electroluminescent organic material of the present invention can preferentially be used as twinkler, comprises separately as luminescent layer, or as the dyestuff of doping and luminous.Also can be used as transport material, comprise as hole-injecting material and hole mobile material simultaneously.
Utilize organic EL device prepared by electroluminescent material of the present invention can show the high-performances such as high brightness, high-level efficiency and low driving voltage.
Number of chemical reaction can be used as in the present invention 1, the synthetic method of 2-benzo [a] anthracene derivant.According to the constructional feature of the compounds of this invention, can take the method for the reaction equation enumerated to prepare below of the present invention various 1,2-benzo [a] anthracene derivant.
Figure G2009100903799D00311
7-halo-1,2-benzo [a] anthracene (compd A) can be by 1,2-benzo [a] anthracene and suitable halogenating agent as N-bromo-succinimide (NBS), N-N-iodosuccinimide (NIS), bromine (Br 2), the reaction such as potassiumiodide or iodine obtains.7-halo 1, the halogen atom X in 2-benzo [a] anthracene 1preferentially be selected from bromine or iodine.
Figure G2009100903799D00312
Compound C can be by compd B and suitable halogenating agent as N-bromo-succinimide (NBS), N-N-iodosuccinimide (NIS), bromine (Br 2), the reaction such as potassiumiodide or iodine obtains.At suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., Compound C and aromatic perfume amine A 1-NH 2or A 2-NH 2there is linked reaction and can obtain Compound D or compd E.In formula (A-1), the halogen atom X in Compound C 2preferentially be selected from bromine or iodine.R 31be selected from respectively the aromatic group that there is the alkane of 1～6 nucleus carbon atom or there are 6～25 nucleus carbon atoms; R 32be selected from respectively hydrogen atom, there is alkane or the alcoxyl hydrocarbon of 1～6 nucleus carbon atom, there is the aromatic group of 6～25 nucleus carbon atoms.
Figure G2009100903799D00321
At suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., carbazole and derivative compound F thereof and dihalo aromatic compound X 2-L 2-X 3there is linked reaction and can obtain compound G; Equally, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., compound G and aromatic perfume amine A 1-NH 2or A 2-NH 2there is linked reaction and can obtain compound H or Compound I.In formula (A-2), X 2-L 2-X 3in halogen atom X 2and X 3preferentially be selected from bromine or iodine, X 2and X 3can be identical, also can be different.L 2for thering is the arylene group of 6～25 nucleus carbon atoms; R 21and R 22select alone respectively hydrogen atom, there is alkane or the alcoxyl hydrocarbon of 1～6 nucleus carbon atom, there is the aromatic group of 6～25 nucleus carbon atoms.
Figure G2009100903799D00322
At suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., aryl secondary amine compound J and dihalo aromatic compound X 4-L 1-X 5there is linked reaction and can obtain compound K; Equally, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., compound K and aromatic perfume amine A 1-NH 2or A 2-NH 2there is linked reaction and can obtain compound L or compound M.In formula (A-3), X 4-L 1-X 5in halogen atom X 4and X 5preferentially be selected from bromine or iodine, X 4and X 5can be identical, also can be different.L 1for thering is the arylene group of 6～25 nucleus carbon atoms; Ar wherein 11and Ar 12be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms.
Figure G2009100903799D00331
Formula (A-4)), in, compound O can be by compound N and suitable phosphoric acid or phosphorous acid ester, as the reactions such as trimethyl phosphite 99, triethyl phosphate or trimethyl phosphite, triethyl-phosphite prepare; Compound Q can by compound O and compound P suitable alkali as conditions such as sodium hydride, potassium hydride KH, sodium ethylate, sodium tert-butoxide and potassium tert.-butoxides under condensation reaction prepare;
Figure G2009100903799D00332
Formula (A-5)), in, compound S can be by compound R and suitable phosphoric acid or phosphorous acid ester, as the reactions such as trimethyl phosphite 99, triethyl phosphate or trimethyl phosphite, triethyl-phosphite prepare; Compound Q can by compound S and compound T suitable alkali as conditions such as sodium hydride, potassium hydride KH, sodium ethylate, sodium tert-butoxide and potassium tert.-butoxides under condensation reaction prepare;
Formula (A-6)) in, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., compound Q and aromatic perfume amine A 1-NH 2or A 2-NH 2there is linked reaction and can obtain compound U or compound V.
In formula (A-4)～(A-6), Ar 41～Ar 43be selected from alone respectively hydrogen atom, there is the alkane of 1～6 nucleus carbon atom or there is the aromatic group of 6～25 nucleus carbon atoms; L 3for thering is the arylene group of 6～25 nucleus carbon atoms; Halogen atom X 5, X 6and X 7preferentially be selected from chlorine, bromine or iodine.
Formula (B-1)) in, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., linked reaction occurs for compd A and aromatic amine compound D or E can obtain corresponding compound V-1a or compound V-1b.R 31be selected from respectively the aromatic group that there is the alkane of 1～6 nucleus carbon atom or there are 6～25 nucleus carbon atoms; R 32be selected from respectively hydrogen atom, there is alkane or the alcoxyl hydrocarbon of 1～6 nucleus carbon atom, there is the aromatic group of 6～25 nucleus carbon atoms.Halogen atom X 1preferentially be selected from bromine or iodine.
Formula (B-2)) in, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., linked reaction occurs for compd A and aromatic amine compound H or I can obtain corresponding compound V-2a or compound V-2b.R 21and R 22select alone respectively hydrogen atom, there is alkane or the alcoxyl hydrocarbon of 1～6 nucleus carbon atom, there is the aromatic group of 6～25 nucleus carbon atoms.Halogen atom X 1preferentially be selected from bromine or iodine.
Figure G2009100903799D00351
Formula (B-3)) in, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., linked reaction occurs for compd A and aromatic amine compound L or M can obtain corresponding compound V-3a or compound V-3b.L 1for thering is the arylene group of 6～25 nucleus carbon atoms; Ar wherein 11and Ar 12be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms.Halogen atom X 1preferentially be selected from bromine or iodine.
Figure G2009100903799D00352
Formula (B-4)) in, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., linked reaction occurs for compd A and aromatic amine compound U or V can obtain corresponding compound V-4a or compound V-4b.L 3for thering is the arylene group of 6～25 nucleus carbon atoms; Ar 41～Ar 43be selected from alone respectively hydrogen atom, there is the alkane of 1～6 nucleus carbon atom or there is the aromatic group of 6～25 nucleus carbon atoms; Halogen atom X 1preferentially be selected from bromine or iodine.
Figure G2009100903799D00361
In formula (A '-1), 7-nitro benzo [a] anthracene through suitable reductive agent as Fe/FeBr 3, the reduction such as Zn/ ammoniacal liquor, Zn/ glacial acetic acid, Pd/C can obtain compd A '.
Figure G2009100903799D00362
In formula (B '-1), at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., compd A ' with halogenated aromatic compd A 1-X 8there is linked reaction and obtain compd B '; Equally, at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, under the catalysis of cuprous iodide etc., compd B ' with halogenated aromatic compd A 2-X 9there is linked reaction and obtain compound V-5.Halogen atom X 8or X 9preferentially be selected from bromine or iodine.Work as A 1=A 2time, and halogenated aromatic compd A 1-X 8and A 2-X 9when identical, compound V-5 at suitable metal catalyst as palladium catalyst, metal catalyst, as copper, or metal compound as catalyst, as can a step coupling under the catalysis of cuprous iodide etc. and obtain.
In above-mentioned reaction formula (A-1)～(A-6), (B-1)～(B-4) and (A '-1), (B '-1), A 1and A 2be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms, or be selected from below general formula (1-1) to the substituted radical of (1-4) representative:
Figure G2009100903799D00363
Figure G2009100903799D00371
Ar wherein 11and Ar 12be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms; L 1for thering is the arylene group of 6～25 nucleus carbon atoms; R 21and R 22select alone respectively hydrogen atom, there is alkane or the alcoxyl hydrocarbon of 1～6 nucleus carbon atom, there is the aromatic group of 6～25 nucleus carbon atoms; L 2for thering is the arylene group of 6～25 nucleus carbon atoms; R 31be selected from respectively the aromatic group that there is the alkane of 1～6 nucleus carbon atom or there are 6～25 nucleus carbon atoms; R 32be selected from respectively hydrogen atom, there is alkane or the alcoxyl hydrocarbon of 1～6 nucleus carbon atom, there is the aromatic group of 6～25 nucleus carbon atoms; Ar 41～Ar 43be selected from respectively hydrogen atom, there is the alkane of 1～6 nucleus carbon atom or there is the aromatic group of 6～25 nucleus carbon atoms; L 3for thering is the arylene group of 6～25 nucleus carbon atoms.
Accompanying drawing explanation
Fig. 1: the electroluminescent spectrum figure of device OLED-1～OLED-6
Fig. 2: current efficiency-current density graphic representation of device OLED-1～OLED-6
Fig. 3: power efficiency-current density graphic representation of device OLED-1～OLED-6
Embodiment
With reference to the following examples, more specifically describe the present invention, but the present invention is not limited to these embodiment.
The synthetic example of compound of the present invention below:
Except special instruction, raw material, intermediate used in the present invention are commercial goods.
The preparation of part intermediate:
(1) 7-is bromo-1, the preparation of 2-benzo [a] anthracene (M1)
Figure G2009100903799D00372
In 1000ml there-necked flask, by 35 grams of (147.4mmol) 1,2-benzo [a] anthracene is dissolved in 550ml N, and N-dimethyl sulfoxide (DMSO) (DMF) is separately dissolved in 140ml DMF by 32.8 grams of (184.4mmol) N-bromo-succinimides (NBS).Under room temperature and magnetic agitation, by constant pressure funnel, this NBS solution is added drop-wise in reaction flask, within approximately 30 minutes, adds.Continue reaction 2 hours, TLC monitors reaction end.By reaction solution forward in beaker, under rapid stirring, drip 400ml water, after fully stirring, the yellow mercury oxide that suction filtration is separated out, water, dehydrated alcohol drip washing successively, dry, obtain 35.8 grams of Melon yellow look solids, yield: 78%.
(2) 7-amino-1, the preparation of 2-benzo [a] anthracene (M2)
To being equipped with in the 1000ml there-necked flask of efficient backflow prolong, add 19.1 grams of (70mmol) 7-amino-1,2-benzo [a] anthracene and 500ml 78% ethanol, the solution that 5 grams of calcium chloride and 8ml water are made into adds in the lump together with 150 grams of zinc powders, and total overall reaction thing is fully mixed.Heating reflux reaction is more than 2 hours.Slightly cooling, elimination zinc mud and zinc oxide, wash by 50ml 78% ethanol extraction while hot.Merging filtrate and extraction washing lotion, slowly in impouring 1000ml water, obtain sundown precipitation under stirring.Suction filtration, filter cake, with appropriate 50% ethyl alcohol recrystallization, obtains 11 grams, sundown crystal, yield: 65%.
The preparation of (3) 1,1-phenylbenzene-2-(4-bromophenyl) ethene (M3)
500ml single port bottle, adds bromine bromobenzyl 45.0g (180mmol), and trimethyl phosphite 32ml (270mmol) adds the reflux condensing tube of calcium chloride tube, heating reflux reaction 4h.The trimethyl phosphite that pressure reducing and steaming is excessive, cooling, obtain 49.8 grams of white solids, yield 99%.
In the 1000ml there-necked flask of nitrogen protection, add step gained to bromobenzyl dimethyl phosphonate 49.8g (166.5mmol), benzophenone 28.5g (151.8mmol), dry THF 220ml.By sodium hydride 10.4g (249.1mmol), divide 4～8 batches and add in reaction system, finish, stirring at room is more than 1 hour, more slowly careful reflux 20h.Stopped reaction, cooling carefully adds methyl alcohol 15ml to remove to removing excessive sodium hydride in system, add each 300ml of ethyl acetate and water, fully stir separatory, water, with ethyl acetate 50ml*2 extraction, merges organic phase, and 100ml washes once, anhydrous magnesium sulfate drying, filters, and filtrate is spin-dried for, the thick product of gained is with 550ml recrystallizing methanol, white needle-like crystals, 36g, yield 65%.
(4) preparation of N-(to bromophenyl) carbazole (M4)
Figure G2009100903799D00391
By 5.90 grams of (25mmol) paradibromobenzenes, 4.15 grams of (24mmol) carbazoles, 4.29 grams of (24mmol) cupric iodides, 6.26 grams of (45mmol) Anhydrous potassium carbonates, 0.79 gram of (3mmol) 18-hat-6 and 70ml 1, 3-DMPU (DMPU) is put in 250ml there-necked flask, under argon shield, reflux 5 hours, be chilled to room temperature, under good stirring, slowly drip water, add and continue again to stir 30 minutes, the solid that suction filtration is separated out, washing, with chloroform, dissolve gained solid, cross quick post, concentrated, add ethanol, the solid that suction filtration is separated out, obtain 6.96 grams of white solids, yield 90%.
(5) preparation of 3-bromine-N-phenylcarbazole (M5)
Figure G2009100903799D00392
Synthesizing of the same N-of synthetic method (to the bromophenyl) carbazole of N-phenyl carbazole, just changes paradibromobenzene into bromobenzene, obtains 29.6 grams of white solids, yield 96%.
In 1000ml there-necked flask, 29.16 grams of (120mmol) N-phenyl carbazoles are dissolved in to 240ml DMF, separately 21.36 grams of (120mmol) NBS are dissolved in to 60ml DMF.Under the cooling and magnetic agitation of ice-water bath, by constant pressure funnel, this NBS solution is added drop-wise in reaction flask, keeps temperature in 0 ℃ of left and right, within approximately 40 minutes, add.Continue room temperature reaction and spend the night, TLC monitors reaction end.Under rapid stirring, in reaction mixture, be added dropwise to 300ml water, after fully stirring, the yellow mercury oxide that suction filtration is separated out, gained crude product is with toluene recrystallization 3 times, 17.4 grams of white solids, yield: 45%.
(6) preparation of the bromo-N-of 3-(2-naphthyl) carbazole (M6)
Figure G2009100903799D00393
Method is synthetic with 3-bromine-N-phenylcarbazole (M5), just changes bromobenzene into 2-bromonaphthalene, obtains 29.6 grams of white solids, total recovery 65%.
(7) preparation to bromophenyl-1-naphthalene (M7)
Figure G2009100903799D00401
In the 250ml there-necked flask of nitrogen protection; add 5.66 grams (20mmol) to bromo-iodobenzene, 8.94 grams of 1-naphthalene boronic acids (52mmol), 0.11 gram of (0.6mmol) Palladous chloride, 0.32 gram of (1.2mmol) triphenylphosphine, 13.8 grams of (100mmol) Anhydrous potassium carbonates, 85ml toluene, 85ml ethanol, 30ml water; magnetic agitation heating reflux reaction 5 hours, TLC monitors reaction end.Cooling, separatory, rotation boils off solvent, then underpressure distillation separating-purifying, obtains 4.25 grams of colorless solids, yield 75%.
(8) preparation of bromophenyl-1-naphthalene (M8) between
Figure G2009100903799D00402
Synthetic with to bromophenyl-1-naphthalene (M7) of method, just will change a bromo-iodobenzene into bromo-iodobenzene, and aftertreatment is without underpressure distillation, and recrystallization obtains 6.7 grams of white solids, yield 83%.
(9) preparation of N-phenyl-N-(1-naphthyl) para-bromoaniline (M9)
Figure G2009100903799D00403
16.98 grams (60mmol) are put in 1000ml there-necked flask bromo-iodobenzene, 13.16 grams of (60mmol) N-phenyl-1-naphthylamines, 0.385 gram of (6mmol) activated copper powder, 24.84 grams of (180mmol) Anhydrous potassium carbonates, 0.79 gram of (3mmol) 18-hat-6 and 350ml orthodichlorobenzene; under argon shield, reflux 24 hours.Be chilled to room temperature, filter pressure reducing and steaming solvent, silica gel column chromatography separating-purifying, ethyl acetate: sherwood oil=1: 20 (volume ratio) wash-out, obtains 8.98 grams of white solids, yield 35%.
(10) preparation of N-phenyl-N-(2-naphthyl) para-bromoaniline (M10)
Figure G2009100903799D00411
Method, with N-phenyl-N-(1-naphthyl) para-bromoaniline (M9), just changes N-phenyl-1-naphthylamine into N-phenyl-2-naphthylamine, obtains 11.3 grams of white solids, yield 46%.
(11) preparation of N-distich phenylaniline (M11)
Figure G2009100903799D00412
9.32 grams of (40mmol) 4-bromo biphenyls, 3.72 grams of (45mmol) aniline, 0.45 gram of (2mmol) palladium, 1.06 grams of (4mmol) triphenyl phosphorus, 13.45 grams of (140mmol) sodium tert-butoxides and 130ml dry toluene are put in 250ml there-necked flask to argon shield lower magnetic force stirring and refluxing reaction 8 hours.Be chilled to room temperature, add moisture liquid, organic phase, with anhydrous magnesium sulfate drying, is filtered, and concentrating under reduced pressure, adds sherwood oil, and the solid that after fully stirring, filtration under diminished pressure is separated out is dry, obtains 7.85 grams, light brown crystal, yield 80%.
The preparation of (12) two (to xenyl) amine (M12)
Figure G2009100903799D00413
Method, with the preparation of N-distich phenylaniline (M11), just changes aniline into 4-amido biphenyl, obtains 9.55 grams of brown purple solids, yield 88%.
(13) preparation of N-(9-phenanthryl) aniline (M13)
Figure G2009100903799D00414
Method, with the preparation of N-distich phenylaniline (M11), just changes 4-bromo biphenyl into 9-bromine luxuriant and rich with fragrance, obtains 8.50 grams of brown purple solids, yield 70%.
(14) N-[is to (1,1-phenylbenzene-2-vinyl) phenyl] preparation of para-biphenylamine (M14)
Method, with the preparation of two (to xenyl) amine (M12), just changes 4-bromo biphenyl into 1,1-phenylbenzene-2-(4-bromophenyl) ethene (M3), obtains 10.30 grams of brown color solids, yield 75%.
(15) N-[is to (N-carbazyl) phenyl]] preparation of para-biphenylamine (M15)
Figure G2009100903799D00422
Method, with the preparation of two (to xenyl) amine (M12), just changes 4-bromo biphenyl into N-(to bromophenyl) carbazole (M4), and catalyst acetic acid palladium changes two (dibenzalacetone) palladium (0) (Pd (dba) into 2), obtain 7.20 grams of brown color solids, yield 60%.
(16) preparation of N-(to triphenylamine base) para-biphenylamine (M16)
Figure G2009100903799D00423
Method, with the preparation of two (to xenyl) amine (M15), just changes N-(to bromophenyl) carbazole (M4) into 4-bromine triphenylamine, obtains 6.80 grams of yellow solids, yield 55%.
(17) preparation of N-(N '-phenyl-3-carbazyl) para-biphenylamine (M17)
Figure G2009100903799D00424
Method, with the preparation of two (to xenyl) amine (M15), just changes N-(to bromophenyl) carbazole (M4) into 3-bromine-N-phenylcarbazole (M5), obtains 10.85 grams of light yellow solids, yield 90%.
(18) N-[is to (1-naphthyl) phenyl] preparation of aniline (M18)
Method is with the preparation of two (to xenyl) amine (M12), just 4-bromo biphenyl and 4-phenylaniline are changed into respectively bromophenyl-1-naphthalene (M7) and aniline, catalyst acetic acid palladium and triphenyl phosphorus change respectively two (dibenzalacetone) palladium (0) (Pd (dba) into 2) and tri-butyl phosphine, obtain 7.75 grams of light yellow solids, yield 88%.
(19) (1-naphthyl) phenyl between N-[] preparation of aniline (M19)
Figure G2009100903799D00432
Method with N-[to (1-naphthyl) phenyl] preparation of aniline (M18), just will change bromophenyl-1-naphthalene (M8) into bromophenyl-1-naphthalene (M7), obtain 6.55 grams of yellow solids, yield 75%.
(20) N-[to (N '-phenyl-N '-(1-naphthyl) amino-benzene] preparation to cyclohexyl aniline (M20)
Figure G2009100903799D00433
Method with N-[to (1-naphthyl) phenyl] preparation of aniline (M18), just will to bromophenyl-1-naphthalene (M7) and aniline changes respectively N-phenyl-N-(1-naphthyl) para-bromoaniline (M9) into and to cyclohexyl aniline, obtain 6.20 grams of yellow solids, yield 50%.
(21) N-[to (N '-phenyl-N '-(2-naphthyl) amino-benzene] preparation of para-biphenylamine (M21)
Method with N-[to (N '-phenyl-N '-(1-naphthyl) amino-benzene] preparation to cyclohexyl aniline (M20), just by N-phenyl-N-(1-naphthyl) para-bromoaniline (M9) with to cyclohexyl aniline, change respectively N-phenyl-N-(2-naphthyl) para-bromoaniline (M10) and 4-phenylaniline into, obtain 6.85 grams of yellow solids, yield 63%.
(22) N-is to [N '-phenyl-N '-(1-naphthyl) amino] phenyl-1, the preparation of 2-benzo [a] anthracene (M22)
Figure G2009100903799D00441
Method with N-[to (1-naphthyl) phenyl] preparation of aniline (M18), just will change respectively N-phenyl-N-(1-naphthyl) para-bromoaniline (M9) and 7-amino-1 into bromophenyl-1-naphthalene (M7) and aniline, 2-benzo [a] anthracene (M2), obtain 3.25 grams of deep yellow solids, yield 46%.
Synthesizing of target compound of the present invention:
Embodiment mono-compound V3's is synthetic
Under argon shield; in 50mL there-necked flask, add 1.22 grams of (5mmol) M2,1.44 grams of (15mmol) sodium tert-butoxides, 2.22 grams of (12mmol) 2,4-dimethyl bromobenzene, 0.029 gram of (0.05mmol) two (dibenzalacetone) palladium (0) (Pd (dba) 2), 0.20 gram of (0.1mmol) tri-butyl phosphine (10% quality toluene solution) and dry toluene 30ml, magnetic agitation back flow reaction 5 hours, TLC monitors reaction end.Cooling, washing, separatory, rotation boils off solution, silica gel column chromatography separating-purifying, ethyl acetate: sherwood oil=1: 12 (volume ratio) wash-out, obtains 1.65 grams of yellow solids, yield 73%.
Product FD-MS (m/z): 451.0, corresponding to: C 34h 29n=451.6, ultimate analysis: C 34h 29n, theoretical value: C, 90.43; H, 6.47; N, 3.10; Experimental value: C, 90.38; H, 6.40; N, 3.11; Prove that this compound is target product V3.
Embodiment bis-compound V8's is synthetic
Figure G2009100903799D00451
Under argon shield, in 50mL there-necked flask, add 1.84 grams of (5mmol) M1,1.44 grams of (15mmol) sodium tert-butoxides, 1.47 grams of (6mmol) N-distich phenylanilines (M11), 0.029 gram of (0.05mmol) two (dibenzalacetone) palladium (0) (Pd (dba) 2), 0.20 gram of (0.1mmol) tri-butyl phosphine (10% quality toluene solution) and dry toluene 35ml, magnetic agitation back flow reaction 2 hours, TLC monitors reaction end.Cooling, washing, separatory, rotation boils off solution, silica gel column chromatography separating-purifying, ethyl acetate: sherwood oil=1: 15 (volume ratio) wash-out, obtains 2.12 grams of yellow solids, yield 90%.
Product FD-MS (m/z): 471.1, corresponding to: C 36h 25n=471.59, ultimate analysis: C 36h 25n, theoretical value: C, 91.69; H, 5.34; N, 2.97; Experimental value: C, 91.60; H, 5.27; N, 2.91; Prove that this chemical combination is target product V8.
Embodiment tri-compound V11's is synthetic
Method is synthetic with embodiment bis-V8's, just changes M11 into M13, obtains 1.75 grams of deep yellow solids, yield 45%.
Product FD-MS (m/z): 495.3, corresponding to: C 38h 25n=495.61, ultimate analysis: C 38h 25n, theoretical value: C, 92.09; H, 5.08; N, 2.83; Experimental value: C, 92.09; H, 5.08; N, 2.83; Prove that this chemical combination is target product V11.
Embodiment Four Modernizations compound V83's is synthetic:
Figure G2009100903799D00461
Method is synthetic with embodiment bis-V8's, just changes M11 into M15, obtains 1.93 grams of glassy yellow solids, yield 53%.
Product FD-MS (m/z): 636.5, corresponding to: C 48h 32n 2=636.78, ultimate analysis: C 48h 32n 2, theoretical value: C, 90.54; H, 5.07; N, 4.40; Experimental value: C, 90.50; H, 5.00; N, 4.31; Prove that this chemical combination is target product V83.
Embodiment five compound V101's is synthetic
Figure G2009100903799D00462
Method is synthetic with embodiment bis-V8's, just changes M11 into M14, obtains 2.34 grams of glassy yellow solids, yield 78%.
Product FD-MS (m/z): 649.5, corresponding to: C 50h 35n=649.82, ultimate analysis: C 50h 35n, theoretical value: C, 92.42; H, 5.43; N, 2.16; Experimental value: C, 92.38; H, 5.40; N, 2.11; Prove that this chemical combination is target product V101.
Embodiment six compound V112's is synthetic
Figure G2009100903799D00471
Method is synthetic with embodiment bis-V8's, just changes M11 into M16, obtains 1.33 grams of orange red solids, yield 36%.
Product FD-MS (m/z): 638.4, corresponding to: C 48h 34n 2=638.80, ultimate analysis: C 48h 34n 2, theoretical value: C, 90.25; H, 5.36; N, 4.39; Experimental value: C, 90.20; H, 5.32; N, 4.31; Prove that this chemical combination is target product V112.
Embodiment seven compound V115's is synthetic
Figure G2009100903799D00472
Method is synthetic with embodiment bis-V8's, just changes M11 into M17, obtains 1.92 grams of orange/yellow solid, yield 75%.
Product FD-MS (m/z): 636.4, corresponding to: C 48h 32n 2=636.78, ultimate analysis: C 48h 32n 2, theoretical value: C, 90.54; H, 5.07; N, 4.40; Experimental value: C, 90.50; H, 5.01; N, 4.35; Prove that this chemical combination is target product V115.
Embodiment eight compound V122's is synthetic
Figure G2009100903799D00481
Method is synthetic with embodiment mono-V3's, just changes 2,4-dimethyl bromobenzene into 4-bromo-4 ', 4 "-dimethyltrianiline, obtain 1.46 grams of dark red solid, yield 40%.
Product FD-MS (m/z): 785.9, corresponding to: C 58h 47n 3=786.01, ultimate analysis: C 58h 47n 3, theoretical value: C, 88.63; H, 6.03; N, 5.35; Experimental value: C, 88.59; H, 6.00; N, 5.34; Prove that this chemical combination is target product V122.
Embodiment nine compound V137's is synthetic:
Method is synthetic with embodiment mono-V3's, just changes 2,4-dimethyl bromobenzene into M7, obtains 1.99 grams of glassy yellow solids, yield 78%.
Product FD-MS (m/z): 785.7, corresponding to: C 50h 33n=786.01, ultimate analysis: C 50h 33n, theoretical value: C, 92.70; H, 5.13; N, 2.16; Experimental value: C, 92.65; H, 5.06; N, 2.12; Prove that this chemical combination is target product V122.
Embodiment ten compound V142's is synthetic
Method is synthetic with embodiment mono-V3's, just changes 2,4-dimethyl bromobenzene into M3, obtains 2.38 grams of glassy yellow solids, yield 88%.
Product FD-MS (m/z): 751.6, corresponding to: C 58h 41n=751.98, ultimate analysis: C 58h 41n, theoretical value: C, 92.64; H, 5.50; N, 1.86; Experimental value: C, 92.60; H, 5.44; N, 1.85; Prove that this chemical combination is target product V142.
Embodiment 11 compound V145's is synthetic:
Figure G2009100903799D00492
Method is synthetic with embodiment bis-V8's, just changes M11 into M18, obtains 1.55 grams of yellow solids, yield 68%.
Product FD-MS (m/z): 521.4, corresponding to: C 40h 27n=521.65, ultimate analysis: C 40h 27n, theoretical value: C, 92.10; H, 5.22; N, 2.69; Experimental value: C, 92.04; H, 5.19; N, 2.62; Prove that this chemical combination is target product V145.
Embodiment 12 compound V151's is synthetic:
Figure G2009100903799D00493
Method is synthetic with embodiment bis-V8's, just changes M11 into M19, obtains 1.31 grams of yellow solids, yield 60%.
Product FD-MS (m/z): 521.2, corresponding to: C 40h 27n=521.65, ultimate analysis: C 40h 27n, theoretical value: C, 92.10; H, 5.22; N, 2.69; Experimental value: C, 92.08; H, 5.21; N, 2.60; Prove that this chemical combination is target product V151.
Embodiment 13 compound V223's is synthetic:
Method is synthetic with embodiment bis-V8's, just changes M11 into M20, obtains 1.08 grams of yellow solids, yield 35%.
Product FD-MS (m/z): 694.7, corresponding to: C 52h 42n 2=694.90, ultimate analysis: C 52h 42n 2, theoretical value: C, 89.88; H, 6.09; N, 4.03; Experimental value: C, 89.85; H, 6.01; N, 4.05; Prove that this chemical combination is target product V223.
Embodiment ten Four Modernizations compound V228's is synthetic
Method is synthetic with embodiment bis-V8's, just changes M11 into M21, obtains 1.36 grams of yellow solids, yield 47%.
Product FD-MS (m/z): 688.5, corresponding to: C 56h 36n 2=688.86, ultimate analysis: C 56h 36n 2, theoretical value: C, 90.67; H, 5.27; N, 4.07; Experimental value: C, 90.60; H, 5.22; N, 4.05; Prove that this chemical combination is target product V228.
Embodiment 15 compound V250's is synthetic
Figure G2009100903799D00511
Method is synthetic with embodiment bis-V8's, just changes respectively M1 and M11 into M4 and M22, obtains 1.69 grams of red solid, yield 51%.
Product FD-MS (m/z): 777.8, corresponding to: C 58h 39n 3=777.95, ultimate analysis: C 58h 39n 3, theoretical value: C, 89.55; H, 5.05; N, 5.40; Experimental value: C, 89.50; H, 5.02; N, 5.48; Prove that this chemical combination is target product V250.
Embodiment 16 compound V255's is synthetic
Method is synthetic with embodiment 15 V250's, just changes M4 into M3, obtains 1.73 grams of yellow solids, yield 59%.
Product FD-MS (m/z): 790.7, corresponding to: C 60h 42n 2=790.99, ultimate analysis: C 60h 42n 2, theoretical value: C, 91.11; H, 5.35; N, 3.54; Experimental value: C, 91.15; H, 5.30; N, 3.62; Prove that this chemical combination is target product V255.
Embodiment 17 compound V265's is synthetic
Figure G2009100903799D00521
Method is synthetic with embodiment 15 V250's, just changes M4 into M6, obtains 1.95 grams of orange/yellow solid, yield 64%.
Product FD-MS (m/z): 827.6, corresponding to: C 62h 41n 3=828.01, ultimate analysis: C 62h 41n 3, theoretical value: C, 89.93; H, 4.99; N, 5.07; Experimental value: C, 89.88; H, 5.02; N, 5.10; Prove that this chemical combination is target product V265.
Other compound of the present invention all can obtain by the method providing in the present invention is synthetic.Following table 1 is mass spectrum and the ultimate analysis data of part of compounds in the present invention:
Table 1
Figure G2009100903799D00522
Figure G2009100903799D00531
Figure G2009100903799D00541
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 be used 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 (SnO 2), zinc oxide (ZnO) etc.In element manufacturing of the present invention, select glass substrate, ITO makes anode material.
Hole transmission layer can adopt N, N '-bis-(3-tolyl)-N, N '-phenylbenzene-[1,1-xenyl]-4,4 '-diamines (TPD) or N, N '-phenylbenzene-N, N '-bis-(1-naphthyl)-(1,1 '-xenyl)-4, the tri-arylamine group materials such as 4 '-diamines (NPB).Wherein NPB is conventional hole mobile material, and hole mobile material selected in element manufacturing of the present invention is selected NPB.
Device architecture can be also multi-luminescent layer structure for single-shot photosphere; Every layer of luminescent layer can be also doped structure for single-shot light body luminescent material structure; Luminescent dye can select fluorescent material also can select phosphor material; Glow color is not limit, can for as red, yellow, blue, green etc.In element manufacturing of the present invention, selected luminescent material is the compounds of this invention V255.
Electric transmission layer material is used 4,7-phenylbenzene-1,10-phenanthroline (BPhen) and Alq conventionally 3, in element manufacturing of the present invention, use Alq 3.
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., can be also electron injecting layer/metal-layer structure, as LiF/Al, Li 2the common cathode construction such as O, wherein electron injecting layer can be simple substance, compound or the mixture of basic metal, alkaline-earth metal, transition metal, can be also the composite cathode structure that multilayer material forms.In element manufacturing of the present invention, selected cathode material is Mg:Ag/Ag.
In the present invention, in device embodiment, different materials structural formula used is as follows:
Figure G2009100903799D00551
Preparation and the result of embodiment 18 El elements
Preparation OLED-1: will be coated with sheet glass supersound process in commercial clean-out system of ITO transparency conducting layer, in deionized water, rinse, at acetone: ultrasonic oil removing in alcohol mixed solvent, under clean environment, be baked to and remove moisture content completely, by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface.
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 * 10 -5～9 * 10 -3pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation speed is 0.1nm/s, and evaporation thickness is 50nm;
Vacuum evaporation one deck BADN on hole transmission layer, this compound is as luminescent material, and its evaporation speed is 0.1nm/s, and evaporation total film thickness is 50nm; Meanwhile, on NNPA, evaporation one deck, as the compounds of this invention V255 of luminescent material, makes BADN: the relative mass of V255 is 99: 1.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, 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 Mg:Ag alloy layer doping ratio be 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 BADN and V255, can make respectively OLED-2～OLED-4, change V255 into TPA, can make OLED-5 and OLED-6.
Device performance is in Table 1 and accompanying drawing 1～3 (device architecture: ITO/NPB/ luminescent layer film/Alq 3/ Mg:Ag/Ag, luminescent layer film composition sees the following form 2):
Table 2
Device sequence number Luminescent layer film Require brightness cd/m 2 Driving voltage V Current density A/m 2 Current efficiency cd/A Power efficiency 1m/VV
OLED-1 BADN:V255(1％) 5000 6.86 266.98 18.73 8.58
OLED-2 BADN:V255(2％) 5000 6.75 262.56 19.04 8.86
OLED-3 BADN:V255(4％) 5000 6.72 244.29 20.47 9.57
OLED-4 BADN:V255(8％) 5000 7.07 273.48 18.73 8.58
OLED-5 BADN:TPA(1％) 5000 7.28 454.84 10.99 4.74
OLED-6 BADN:TPA(4％) 5000 7.34 560.51 8.92 3.82
As can be seen from Table 2, in embodiment 18, used luminescent device OLED-1～OLED-4 of the compounds of this invention V255, at identical brightness (5000cd/m 2) under, current efficiency and power efficiency are all apparently higher than the luminescent device that has used contrast material TPA.And the former driving voltage also will be lower than the latter's driving voltage.
Although describe the present invention in conjunction with the embodiments, but the present invention is not limited to above-described embodiment 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 (8)

  1. One kind as shown in following general formula (1) 1,2-benzo ［ a ］ anthracene derivant:
    Figure FDA00003622629200011
    In general formula (1), A 1and A 2independently be selected from respectively general formula (1-1) or (1-4) substituted radical of representative below:
    Figure FDA00003622629200012
    Ar wherein 11and Ar 12independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms, L 1for thering is the arylene group of 6～25 nucleus carbon atoms;
    Ar 41and Ar 42independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms, Ar 43be selected from hydrogen atom or there is the alkane of 1～6 nucleus carbon atom; L 3for thering is the arylene group of 6～25 nucleus carbon atoms.
  2. 2. according to claim 11,2-benzo ［ a ］ anthracene derivant, wherein L 1be selected from phenylene, naphthylidene, phenanthrylene, sub-pyrenyl, Ya perylene base, sub-fluoranthene base, anthrylene, sub indenyl.
  3. 3. according to claim 11,2-benzo ［ a ］ anthracene derivant, A 1and A 2be selected from alone respectively general formula (2-1) or (2-4) substituted radical of representative below:
    Figure FDA00003622629200013
    Ar wherein 11and Ar 12be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms;
    R 11～R 13be selected from alone respectively hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    Ar 41and Ar 42independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms, Ar 43be selected from hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    R 41～R 43be selected from alone respectively hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    In general formula (1), A 1and A 2can be identical, also can be different.
  4. 4. according to claim 11,2-benzo ［ a ］ anthracene derivant, A 1and A 2be selected from alone respectively below general formula (3-1), (3-2), (3-6) or (3-7) substituted radical of representative:
    Figure FDA00003622629200022
    Ar wherein 11and Ar 12independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms;
    Ar 21and Ar 22be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms;
    Ar 61and Ar 62independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms, Ar 63be selected from hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    Ar 71and Ar 72independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms, Ar 73be selected from hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    In general formula (1), A 1and A 2can be identical, also can be different.
  5. 5. according to claim 11,2-benzo ［ a ］ anthracene derivant, molecular structural formula is as follows:
    Figure FDA00003622629200031
    Figure FDA00003622629200041
    Figure FDA00003622629200051
    Figure FDA00003622629200061
  6. 6. compound claimed in claim 1 is applied in organic electroluminescence device, as luminescent material.
  7. 7. an organic electroluminescence device, comprises the first electrode and the second electrode, and the organic function layer between two electrodes, it is characterized in that, at least one deck in organic function layer comprises the compound with following structural:
    Figure FDA00003622629200062
    In general formula (1), A 1and A 2difference is general formula (1-1) or (1-4) substituted radical of representative below alone:
    Figure FDA00003622629200063
    Figure FDA00003622629200071
    Ar wherein 11and Ar 12be selected from alone respectively the aromatic group with 6～25 nucleus carbon atoms;
    L 1for thering is the arylene group of 6～25 nucleus carbon atoms;
    Ar 41and Ar 42independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms, Ar 43be selected from hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    L 3for thering is the arylene group of 6～25 nucleus carbon atoms.
  8. 8. according to the organic electroluminescence device of claim 7, it is characterized in that the A in compound general formula (1) 1and A 2be selected from alone respectively general formula (2-1) or (2-4) substituted radical of representative below:
    Figure FDA00003622629200072
    R 11～R 13be selected from alone respectively hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    Ar 41and Ar 42independently be selected from respectively the aromatic group with 6～25 nucleus carbon atoms, Ar 43be selected from hydrogen atom or there is the alkane of 1～6 nucleus carbon atom;
    R 41～R 43be selected from alone respectively hydrogen atom or there is the alkane of 1～6 nucleus carbon atom.
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