CN100425599C - Organic electroluminescent material and its application - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device comprising the compound. The structure general formula of the compound is as following: n is an integer from one to four; Ar and Ar' are respectively and independently selected from hydrogen atoms, replacing or non-replacing aromatic radical, heterocyclic ring aromatic radical, condensed ring aromatic radical or fused heterocycle aromatic radical. In addition, Ar and Ar' are not simultaneously hydrogen atoms. R1 and R2 are respectively selected from halogen atoms, replacing or non-replacing alkyl group, alkoxyl group, alkyl group of amino group, alkyl sulphide radical, aromatic group or heterocyclic ring aromatic group. The present invention overcomes problems of color purity, luminous efficiency, etc. of the existing generally used luminescent material. The material of the present invention can be preferentially used as a luminous body and is independently used as a luminescent layer or doped dye for emitting light. In addition, the present invention can be used for electronic transmission and hole barrier material simultaneously. The electroluminescent device prepared by utilizing the material of the present invention presents high performance of high color purity, high brightness and high efficiency.

Description

A kind of electroluminescent organic material and application thereof

Technical field

The present invention relates to a kind of electroluminescent organic material, and the application in organic electroluminescence device, the ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field belonged to.

Background technology

Organic electroluminescence device (hereinafter to be referred as organic EL) has a wide range of applications in various fields owing to have that thin, the full curing of ultralight, luminous, response speed are fast, good temp characteristic, can realize characteristic such as soft demonstration.

The research of organic EL starts from nineteen sixties.People (J.Chem.Phys.1963 such as Pope in 1963,38:2042～2043) studied the blue coloured electroluminous of anthracene single crystal sheet (10～20 μ m), restriction because of the thicker and employed electrode materials of anthracene single crystal luminescent layer (elargol and sodium chloride solution), the luminous trigger voltage of device is up to 400V, and efficient and brightness are all lower.Yet a frontier of luminous science and technology has been opened up in this discovery.Between two more than ten years after this, the progress of organic EL is slow.Until 1987, (Appl.Phys.Lett.1987,51:913～915) such as the C.W.Tang of Kodak just obtained the breakthrough with milestone significance.They adopt bilayer structure to do with oxine aluminium (Alq3) that luminescent layer, aromatic diamines are made hole transmission layer, ITO makes the bi-layer devices that anode, Mg: Ag (10: 1) alloy is made negative electrode, obtains higher quantum yield (1%) and luminous efficiency (1.5lm/W): high brightness (＞1000cd/m2) with than the low driving voltage (device of≤10V.This progress has been aroused the hope that organic EL is applied to panchromatic flat-panel monitor again, and the research of material and device becomes the focus of research rapidly.1988, people such as Adchi [J.Appl.Phys.1988,27 (2): L269～L271] released the multilayer sandwich type structural, have expanded the range of choice of organic EL Material greatly.

Through vicennial development, organic EL Material round Realization red, blue, green emitting, Application Areas has also expanded polymer and metal complex field to from small molecules.In theory, it is ripe that the organic electroluminescent technique of display has been tending towards, and some products come into the market, but in the commercialization process, still have many problems to need to be resolved hurrily.Especially for the various organic materialss of making device, its current carrier injects, transmission performance, material electroluminescence performance, work-ing life, purity of color, between each material and and each electrode between coupling etc., many problems are still unresolved.Simultaneously, material new, that performance is more excellent constantly is found and uses, and element manufacturing technology and device performance are being updated among the raising.

The basic structure of organic EL device comprises anode/hole injection and transport layer/organic luminous layer/electron injecting layer/negative electrode, now used organic EL device is mostly because driving voltage is higher, luminosity and efficient are lower, and the performance degradation of device get quite fast, so still be difficult to be applied to actual production.

Summary of the invention

The purpose of this invention is to provide and a kind ofly have excellent luminous efficiency and thermotolerance, the life-span is long and emission has excellent color purity novel electroluminescent material, and the organic electroluminescence device that adopts this material.

After studying for a long period of time, the inventor has found that the Ben Bing oxadiazole compound of ad hoc structure has good thermal stability, high efficiency luminescent properties, easy synthetic method and purification step, subsequently it is applied in the device, resulting device has higher purity of color and efficient.Just be based on this understanding, finishing this invention.

The present invention proposes the compound that the following general formula of a kind of usefulness is represented:

Wherein n is the integer of 1-4, and Ar and Ar ' are independently selected from hydrogen atom respectively, replacement or unsubstituted aryl group, heteroaromatic group, condensed ring aromatic group or fused heterocycle aromatic group, and Ar and Ar ' are not hydrogen atom simultaneously;

R ₁, R ₂Be selected from halogen atom identical or inequality respectively, or be selected from replacement identical or inequality or unsubstituted alkyl, alkoxyl group, alkylamino, alkylthio, aromatic base or heterocyclic aromatic base.

In the said structure formula, Ar and Ar ' are preferably hydrogen atom; Be preferably and contain C _6-20Aryl or substituted aryl, as phenyl, naphthyl, xenyl, p-terphenyl base, anthryl, dianthranide base, to tert-butyl-phenyl, 2,4 difluorobenzene base, 4-(N, N-dimethyl amido) phenyl etc., wherein most preferred is naphthyl, p-terphenyl base, anthryl; Be preferably and contain C _6-20Fused ring aryl such as pyrenyl, naphthacenyl, phenanthryl, benzo phenanthryl, benzanthrene, benzo pyrenyl, fluorenyl etc., wherein most preferred is pyrenyl, benzo anthryl, fluorenyl; Be preferably and contain C _4-20Heterocyclic aryl or fused heterocycle aryl such as pyridyl, quinolyl, benzothienyl, cumarone, indyl, benzimidazolyl-, benzothiazolyl etc., wherein most preferred is pyridyl, quinolyl.

In the said structure formula, R ₁, R ₂Be selected from hydrogen atom, C respectively _1-30Alkyl or substituted alkyl, C _1-30Alkoxyl group or alkoxyl group, the C of replacement _2-30Alkylamino or the alkylamino of replacement, as methyl, trifluoromethyl, ethyl, sec.-propyl, the tertiary butyl, methoxyl group, oxyethyl group, isopropoxy, tertiary butyl oxygen base, N, N-dimethyl amido, N, N-diethyl amido; C _1-30Alkylthio or substituted alkane sulphur base, as methylthio group, ethylmercapto group, sec.-propyl sulfenyl, tertiary butyl sulfenyl; C _6-20Aryl or substituted aryl, C _6-20Fused ring aryl or C _4-20Heterocyclic aryl or fused heterocycle aryl, as phenyl, naphthyl, xenyl, pyrenyl, fluorenyl, pyridyl, quinolyl.

For clearer narration content of the present invention, the narration of following mask body but preferred structure in the type of compounds that is not limited to the present invention relates to.

I, Ar are identical with Ar ', and are aryl or fused ring aryl, the molecular structure symmetry:

Ii, Ar are identical with Ar ', are heterocyclic aryl or fused heterocycle aryl:

Iii, Ar are different with Ar ', respectively are aryl, substituted aryl, heterocyclic aryl or fused heterocycle aryl

Material of the present invention has the following advantages:

Electroluminescent organic material of the present invention can preferentially be used as twinkler, comprises separately as luminescent layer, perhaps as adulterated dyestuff and luminous, and also can be used as electric transmission, hole barrier materials simultaneously.

Utilize the organic electroluminescence device of luminescent material preparation of the present invention can show high purity, high brightness, high efficiency high-performance.

Description of drawings

Fig. 1 is a material 4 of the present invention, 7-two (4 '-xenyl)-2,1, the mass spectrum of 3-Ben Bing oxadiazole (compound i-4);

Fig. 2 is the electroluminescent graph of device OLED-1～OLED-3;

Fig. 3 is the electroluminescent graph of device OLED-4～OLED-5.

Embodiment

Preferred implementation: compound of the present invention all is to adopt aryl or heterocyclic aryl boric acid and dibromo-benzene Bing oxadiazole compounds parent prepared in reaction.

The preparation of raw material aryl boric acid:

Used most of aryl boric acid raw material all is to buy in lark prestige company among the present invention, and dibromo-benzene Bing oxadiazole parent and part aryl boric acid are according to following method synthetic.

Synthesizing of 4-biphenyl boric acid:

Reaction formula:

Process: in being furnished with the 100ml there-necked flask of magnetic agitation, reflux exchanger and nitrogen protection device; 5.83 gram 4-bromo biphenyl (0.025mol) are dissolved in 20mlTHF, add magnesium chips 0.85 gram (0.035mol), the 0.5ml monobromethane; warm making reacted beginning, refluxes 2 hours.(3.25ml 0.03mol) is cooled to-5 ℃ to-10 ℃ with the cryosel bath, and nitrogen protection slowly adds in the Grignard reagent of 4-bromo biphenyl down, and the temperature of keeping reaction flask finishes below 0 ℃, stirs 12 hours under the room temperature with trimethyl borate 3.12 grams.Dripping hydrochloric acid solution (5ml concentrated hydrochloric acid, 15ml water) stirred 30 minutes, use ethyl acetate extraction, tell organic layer, be yellow, water layer is used 2 * 50ml ethyl acetate extraction again, merges organic layer, is washed to neutrality with saturated common salt, anhydrous magnesium sulfate drying, be spin-dried for, get oily liquids, wash with 60ml sherwood oil heat, get 3.2 gram pale pulverulent solids 4-biphenyl boric acid, yield is 65%.

Other aryl boric acid is used with quadrat method synthetic.

The preparation of raw material dibromo-benzene Bing oxadiazole parent:

According to document Oganic Syntheses, Coll.Vol.4,74, Organic Process Research ﹠amp; Development2003,7,1043～1047, Journal of Organic Chemictry, 1974,11,813～814 and Russian Journal ofOrganic Chemictry, 2003,39,957～962 reported method are synthetic.

The structural formula of n=1～4 o'clock each parent is as follows:

(1) parent 1 is synthetic:

I) 2,1,3-Ben Bing oxadiazole-N-oxide compound synthetic:

With 18.0 gram (321mmol) potassium hydroxide, 255mL95% ethanol joins is furnished with in the churned mechanically 1000mL there-necked flask, the stirring heating dissolving.41.7 gram (290mmol) o-Nitranilines are joined in the alkali lye of above-mentioned heat, and stirring and dissolving gets red solution.Stir fast down, this solution cryosel is bathed be cooled to below 0 ℃, keep good and stir down, be added drop-wise to the 375mL chlorine bleach liquor in the reaction system, temperature control is below 5 ℃.Added the back restir 10 minutes.Stop, suction filtration, the washing filter cake dries, and gets yellow solid 36.1 grams, productive rate 91.6%.

Ii) 2,1,3～Ben Bing oxadiazole synthetic:

In being equipped with the 100mL there-necked flask of nitrogen protection device, magnetic stirring apparatus, reflux condensing tube, add 8.8 gram (64.2mmol) Ben Bing oxadiazole-N-oxide compound and 40mL tetrahydrofuran (THF), stirring and dissolving.Under nitrogen protection and the magnetic agitation, slowly drip the solution that 20.8 gram (77.0mmol) triphenylphosphines are dissolved in the 25mL tetrahydrofuran (THF) from constant pressure funnel.Exothermic heat of reaction rises temperature voluntarily.Dropwise, continued stirring reaction 18 hours under the room temperature.Reaction finishes, and carries out steam distillation, till no solid distillates.Collect solid, it is dissolved in the ethanol of 25mL heat, stir down, the ethanolic soln that this is hot slowly joins in the beaker that 120mL distilled water is housed, and separates out a large amount of white precipitates.Filtration under diminished pressure, washing is dried, and gets white solid 4.3 grams, productive rate 55.2%.

Iii) 4,5,6, the 7-tetrabromobisphenol, 1,3 hexanaphthene Bing oxadiazole synthetic:

(101.4mmol) Ben Bing oxadiazole, 100mL Hydrogen bromide (47%) and 27.8mL (506.4mmol) bromine join to be furnished with in the churned mechanically 250mL there-necked flask, 35 ℃ of following stirring reactions 24 hours with 12.1 grams.

Stopped reaction.Reaction mixture is poured in the ice-cold solution of 700mL 5% S-WAT into brown taking off.Suction filtration, the washing solid, dry greyish white solid.With 95% ethyl alcohol recrystallization, 70 ℃ of dryings of vacuum get white needle-like crystals, 30.1 grams, productive rate 67.5%.

Iv) parent 1 is synthetic:

With 5.4 gram (12.0mmol) 4,5,6, the 7-tetrabromobisphenol, 1,3 hexanaphthene Bing oxadiazole, 0.009 gram (0.03mmol) Tetrabutyl amonium bromide and 30mL dimethyl sulfoxide (DMSO) join is furnished with in the churned mechanically 100mL there-necked flask, stirs the low-grade fever dissolving.Keep good and stir down, slowly drip the potassium hydroxide aqueous solution of 30mL50%, add back restir reaction 10 minutes.

Stopped reaction.Separatory.Upper organic phase adds the 100mL ethyl acetate, is washed to neutrality again.Water layer is with ethyl acetate extraction (30mL*2), and washing merges organic phase, anhydrous sodium sulfate drying.The solution that drying is good is that stationary phase is crossed quick post with silica gel, ethyl acetate drip washing, and the rotation solvent evaporated gets pale brown look crystal, with 85% recrystallizing methanol, gets colourless acicular crystal 1.5 grams, productive rate 45.4%.

Reaction formula is as follows:

(2) parent 2 is synthetic:

0.86g (3.1mmol) parent 1 is added in the 100mL there-necked flask, under the nitrogen protection, add 15mL exsiccant THF, be cooled to-78～-80 ℃.Slowly add 1.94mL n-Butyl Lithium (1.6M), stir 30min.Be warming up to-50～-45 ℃, drip 0.427gZnCl again ₂Be dissolved in the solution of 15mL exsiccant THF, add the back and stir and rise to naturally room temperature.Slowly drip by 0.803g (3.1mmol) parent 1 and 0.0018g (0.015mmol) Pd (PPh ₃) ₄Be dissolved in the solution of 20mL exsiccant THF.Add under the room temperature of back and stir 2h.NaOH solution conditioned reaction liquid with 10% is to PH=7～8.Suction filtration is told organic phase, and water layer extracts with ethyl acetate 20mL * 2.Merge organic phase, washing, column chromatography for separation gets white solid 0.42g, yield 35.8%.

Product MS (m/e): 395.9; Ultimate analysis (C ₁₂H ₄Br ₂N ₄O ₂): theoretical value C:36.40, H:1.02, N:14.15; Measured value C:36.32, H:1.99, N:14.03.

Reaction formula is as follows:

(3) parent 3 is synthetic:

Process is with (2), and just except that the amount of the parent 1 of the first step was constant, all corresponding increase of the amount of all the other reagent got final product for 1 times.Get white solid 0.68g, yield 43.2%.

Product MS (m/e): 514.0; Ultimate analysis (C ₁₈H ₆Br ₂N ₆O ₃): theoretical value C:42.05, H:1.18, N:16.35; Measured value C:42.00, H:1.16, N:16.26.

Reaction formula is as follows:

(4) parent 4 is synthetic:

Process is with (3), just changes the raw material parent 1 of the first step into parent 2 and gets final product.Get white solid 0.79g, yield 40.5%.

Product MS (m/e): 632.1; Ultimate analysis (C ₂₄H ₈Br ₂N ₈O ₄): theoretical value C:45.60, H:1.28, N:17.22; Measured value C:45.54, H:1.26, N:17.16.

Reaction formula is as follows:

Be the synthetic embodiment of compound of the present invention below:

Embodiment 1,7-dibiphenylyl-2,1,3-Ben Bing oxadiazole (compound i-4)

Reaction formula:

Process:

Is being furnished with magnetic stirring apparatus; in the 100mL there-necked flask of condensation reflux unit and nitrogen protection device; add 4 successively under the nitrogen atmosphere; 7-dibromo benzo oxadiazole (1.50 grams; 5.2mmol), Anhydrous potassium carbonate (3.59 the gram; 26.0mmol), 4-biphenyl boric acid (2.52 the gram; 12.5mmol), two (triphenylphosphine) palladium chloride (0.70 the gram; 1.0mmol) and the mixing solutions 65mL that forms by toluene, second alcohol and water (volume ratio is 3: 3: 2); reflux under the nitrogen protection was reacted 24 hours.Stop heating, cool to room temperature.

In reaction solution impouring 50mL water, filtration under diminished pressure, water, ethyl acetate drip washing filter cake successively, solid drying is used the toluene recrystallization, yellow product.

Product MS (m/e): 424.2; Ultimate analysis (C ₃₀H ₂₀N ₂O): theoretical value C:85.16, H:4.90, N:6.62; Measured value C:85.13, H:4.90, N:6.57.

Embodiment 24 ,-two (1-naphthyls)-2,1,3-Ben Bing oxadiazole (compound i-5)

Reaction formula:

Process is same as embodiment one, just raw material is changed to the 1-naphthalene boronic acids, gets yellow product.

Product MS (m/e): 372.4; Ultimate analysis (C ₂₆H ₁₆N ₂O): theoretical value C:83.85, H:4.33, N:7.52; Measured value C:83.82, H:4.30, N:7.47.

Embodiment 34,7-two (2-naphthyl)-2,1,3-Ben Bing oxadiazole (compound i-6)

Reaction formula:

Process is same as embodiment one, just raw material is changed to the 2-naphthalene boronic acids, gets yellow product.

Product MS (m/e): 372.4; Ultimate analysis (C ₂₆H ₁₆N ₂O): theoretical value C:83.85, H:4.33, N:7.52; Measured value C:83.80, H:4.31, N:7.48.

Embodiment 44,7-two (9-anthryl)-2,1,3-Ben Bing oxadiazole (compound i-7)

Reaction formula:

Process is same as embodiment one, just raw material is changed to 9-anthracene boric acid, gets yellow product.

Product MS (m/e): 472.5; Ultimate analysis (C ₃₄H ₂₀N ₂O): theoretical value C:86.42, H:4.27, N:5.93; Measured value C:86.40, H:4.26, N:5.87.

Embodiment 54,7-two (2 '-perylene base)-2,1,3-Ben Bing oxadiazole (compound i-9)

Reaction formula:

Process is same as embodiment one, just raw material is changed to 2-perylene boric acid, gets the deep yellow product.

Product MS (m/e): 620.7; Ultimate analysis (C ₄₆H ₂₄N ₂O): theoretical value C:89.01, H:3.90, N:4.51; Measured value C:88.98, H:3.90, N:4.46.

Embodiment 64 ,-two (1 '-pyrenyl)-2,1,3-Ben Bing oxadiazole (compound i-10)

Reaction formula:

Process is same as embodiment one, just raw material is changed to 1-pyrene boric acid, gets light yellow product.

Product MS (m/e): 520.5; Ultimate analysis (C ₃₈H ₂₀N ₂O): theoretical value C:87.67, H:3.87, N:5.38; Measured value C:87.64, H:3.85, N:5.35.

Embodiment 74,7-two (5 '-phenanthryl)-2,1,3-Ben Bing oxadiazole (compound i-11)

Reaction formula:

Process is same as embodiment one, just raw material is changed to the luxuriant and rich with fragrance boric acid of 5-, gets light yellow product.

Product MS (m/e): 472.5; Ultimate analysis (C ₃₄H ₂₀N ₂O): theoretical value C:86.42, H:4.27, N:5.93; Measured value C:86.40, H:4.27, N:5.88.

Embodiment 84,7-two [(4 '-benzyloxy)-4 "-phenyl]-2,1,3-Ben Bing oxadiazole (compound i-12)

Reaction formula:

Process is same as embodiment one, just raw material is changed to 4-benzyloxy phenylo boric acid, gets light yellow product.

Product MS (m/e): 456.4; Ultimate analysis (C ₃₀H ₂₀N ₂O ₃): theoretical value C:78.93, H:4.42, N:6.14; Measured value C:78.91, H:4.41, N:6.09.

Embodiment 94,7-two (4 '-(2 ", 2 "-diphenylacetylene) phenyl-2,1,3-Ben Bing oxadiazole (compound i-13)

Reaction formula:

Process is same as embodiment one, just raw material is changed to 4-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide, Dry Sack look product.

Product MS (m/e): 628.7; Ultimate analysis (C ₄₆H ₃₂N ₂O): theoretical value C:87.87, H:5.13, N:4.46; Measured value C:87.81, H:5.11, N:4.39.

Embodiment 10,7-two (9 ', 9 '-dioctyl fluorene-3 '-)-2,1,3-Ben Bing oxadiazole (compound i-14)

Reaction formula:

Process is same as embodiment one, just raw material is changed to 9, and 9-dioctyl fluorene-3-boric acid gets light yellow product.

Product MS (m/e): 901.4; Ultimate analysis (C ₆₄H ₈₈N ₂O): theoretical value C:85.28, H:9.84, N:3.11; Measured value C:85.23, H:9.84, N:3.17.

Embodiment 11,4 '-two (2,4 difluorobenzene bases)-7,7 '-Lian-2,1,3-benzene and oxadiazole (compound i-15)

Reaction formula:

Process is same as embodiment one, just raw material is changed to parent 2 and 2,4 difluorobenzene boric acid respectively, gets yellow product.

Product MS (m/e): 462.3; Ultimate analysis (C ₂₄H ₁₀F ₄N ₄O ₂): theoretical value C:62.35, H:2.18, N:12.12; Measured value C:62.27, H:2.17, N:12.08.

Embodiment 12,7-two (2 '-quinolyl)-2,1,3-Ben Bing oxadiazole (compound i i-1)

Reaction formula:

Process is same as embodiment one, just raw material is changed to 2-quinoline boric acid, gets light yellow product.

Product MS (m/e): 374.3; Ultimate analysis (C ₂₄H ₁₄N ₄O): theoretical value C:76.99, H:3.77, N:14.96; Measured value C:76.91, H:3.75, N:14.94.

Embodiment 13,7-two [4 '-(2 "-quinolyl) phenyl]-2,1,3-Ben Bing oxadiazole (compound i i-2)

Reaction formula:

Process is same as embodiment one, just the first step raw material is changed to bromobenzene boric acid, and the second step raw material is changed to 2-quinoline boric acid, gets the deep yellow product.

Product MS (m/e): 526.5; Ultimate analysis (C ₃₆H ₂₂N ₄O): theoretical value C:82.11, H:4.21, N:10.64; Measured value C:82.13, H:4.21, N:10.58.

Embodiment 14,7-two [4 '-(4 "-pyridyl) phenyl]-2,1,3-Ben Bing oxadiazole (compound i i-4)

Reaction formula:

Process is same as ten two the second steps of embodiment, just raw material is changed to 4-pyridine boric acid, must light yellow product.

Product MS (m/e): 426.4; Ultimate analysis (C ₂₈H ₁₈N ₄O): theoretical value C:78.86, H:4.25, N:13.14; Measured value C:78.80, H:4.23, N:13.10.

Embodiment 15,7-two (N-phenyl benzindole-3 '-)-2,1,3-Ben Bing oxadiazole (compound i i-5)

Reaction formula:

Process is same as embodiment one, just raw material is changed to N-phenyl benzindole-3-boric acid, gets the deep yellow product.

Product MS (m/e): 502.5; Ultimate analysis (C ₃₄H ₂₂N ₄O): theoretical value C:81.26, H:4.41, N:11.15; Measured value C:81.20, H:4.40, N:11.07.

Embodiment 16,7-two (2 '-thienyl)-2,1,3-Ben Bing oxadiazole (compound i i-6)

Reaction formula:

Process is same as embodiment one, just raw material is changed to thionaphthene-2-boric acid, gets light yellow product.

Product MS (m/e): 384.4; Ultimate analysis (C ₂₂H ₁₂N ₂OS ₂): theoretical value C:68.73, H:3.15, N:7.29; Measured value C:68.70, H:3.15, N:7.32.

Embodiment 17 4-(4 '-xenyl)-7-(9-anthryl)-2,1,3-Ben Bing oxadiazole (compound i ii-1)

Reaction formula:

Process is same as embodiment one, and raw material ratio is 1:1 in the first step, in second step raw material is changed to 9-anthracene boric acid, gets the deep yellow product.

Product MS (m/e): 448.5; Ultimate analysis (C ₃₂H ₂₀N ₂O): theoretical value C:85.69, H:4.49, N:6.25; Measured value C:85.63, H:4.48, N:6.21.

Embodiment 18 4-(4 "-xenyl)-7-[4 "-(2 ", 2 "-diphenylacetylene) phenyl]-2,1,3-Ben Bing oxadiazole (compound i ii-5)

Reaction formula:

Process is same as second step among the embodiment 16, just raw material is changed to 4-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide boric acid, gets the deep yellow product.

Product MS (m/e): 526.6; Ultimate analysis (C ₃₈H ₂₆N ₂O): theoretical value C:86.67, H:4.98, N:5.32; Measured value C:86.62, H:4.99, N:5.27;

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/electron transfer layer (ETL)/negative electrode.

Substrate is transparent, can be glass or flexible substrate, and flexible substrate adopts a kind of material in polyester, the polyimide compounds; Anode layer can adopt inorganic materials or organic conductive polymkeric substance, inorganic materials is generally the higher metals of work function such as metal oxides such as tin indium oxide (hereinafter to be referred as ITO), zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as, organic conductive polymkeric substance are preferably a kind of material in Polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS), the polyaniline (hereinafter to be referred as PANI); Cathode layer generally adopts the alloy of the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold and silver, or the electrode layer that alternately forms of metal and metal fluoride, the present invention is preferably Mg:Ag alloy layer, Ag layer and LiF layer successively, Al layer successively; Hole transmission layer generally adopts the tri-arylamine group material, and the present invention is preferably N, N '-two-(1-naphthyl)-N, N '-phenylbenzene-1,1-xenyl-4,4-diamines (NPB); Electron transfer layer is generally a metal-organic complex, preferably closes gallium (III) (the following Alq that is called for short respectively as three (oxine) aluminium, three (oxine) gallium, (the adjacent amine phenol of salicylidene)-(oxine) ₃, Gaq ₃, Ga (Saph-q)), also can be the o-phenanthroline class, as 4,7-phenylbenzene-1,10-o-phenanthroline (hereinafter to be referred as Bphen) etc., organic luminous layer generally can adopt small molecule material, can doping fluorescent material or phosphorescent coloring, comprised the luminous organic material that the present invention proposes in the organic luminous layer of the present invention, it can be directly luminous, also can be used as dye adulterated luminously in corresponding material of main part, and preferred material of main part is Alq ₃, Gaq ₃, Ga (Saph-q).

Prepare a series of organic electroluminescence device of the present invention in accordance with the following methods:

(1) uses clean-out system, deionized water and organic solution to divide several steps to clean and have the anodic glass substrate;

(2) hole transmission layer of the method evaporation device by vacuum-evaporation;

(3) continue the luminescent layer that evaporation comprises red light material of the present invention again;

(4) electron transfer layer of continuation evaporation device;

(5) method by evaporation or sputter prepares metallic cathode again.

Embodiment 19 fabricate devices OLED-1～OLED-3

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 cleaning machine irradiation 10 minutes, 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 continues evaporation NPB as hole transmission layer on above-mentioned anode tunic, evaporation speed is 0.1nm/s, and the evaporation thickness is 50nm;

On hole transmission layer, continue the Alq that evaporation one deck is doped with compound (i-4) ₃As the luminescent layer of device, compound (i-4) and Alq ₃The evaporation speed ratio be 1: 100, compound (i-4) is at Alq ₃In doping content be 1wt%, the total speed of its evaporation is 0.1nm/s, the evaporation total film thickness is 30nm;

Continue evaporation one deck Alq again ₃Material is as the electron transfer layer of device, and its evaporation speed is 0.1nm/s, and the evaporation total film thickness is 20nm;

At last, evaporation Mg:Ag alloy layer and Ag layer are as the cathode layer of device successively on above-mentioned electron transfer layer, and wherein the evaporation speed of Mg:Ag alloy layer is 2.0-3.0nm/s, and thickness is 100nm, and the evaporation speed of Ag layer is 0.3nm/s, and thickness is 100nm.

Preparing OLED-2 and OLED-3 according to the method described above, only is to have changed compound (i-4) at Alq ₃In doping content, the performance of device sees table 1 for details:

Table 1:

Device number	Device architecture is formed	Emission wavelength nm	Current density A/m 2	Brightness cd/m2	Efficient cd/A
						OLED-1	ITO/NPB(50nm)/Alq 3: 1wt% compound (i-4) (30nm)/Alq 3(20nm)/MgAg:Ag	520	50	98	1.8
OLED-2	ITO/NPB(50nm)/Alq 3: 4wt% compound (i-4) (30nm)/Alq 3(20nm)/MgAg:Ag	520	50	72	1.4
						OLED-3	ITO/NPB(50nm)/Alq 3: 8wt% compound (i-4) (30nm)/Alq 3(20nm)/MgAg:Ag	520	50	26	0.5

Embodiment 20 fabricate devices OLED-4, OLED-5

Method just changes luminescent layer into ii-2 with embodiment 18.The performance of device sees table 2 for details:

Table 2:

Device number	Device architecture is formed	Emission wavelength nm	Current density A/m 2	Brightness cd/m2	Efficient cd/A
						OLED-4	ITO/NPB(50nm)/Alq 3: 1wt% compound (ii-2) (30nm)/Alq 3(20nm)/MgAg:Ag	532	50	230	4.5
OLED-5	ITO/NPB(50nm)/Alq 3: 100wt% compound (ii-2) (30nm)/Alq 3(20nm)/MgAg:Ag	548	50	197	3.8

Although describe the present invention in conjunction with the preferred 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 (7)

1, a kind of compound, general structure is as follows:

Wherein n is the integer of 1-4, and Ar and Ar ' are independently selected from C respectively _6-20Aryl, the C of replacement _6-20Aryl, C _6-20Fused ring aryl, C _4-20Heterocyclic aryl or C _4-20The fused heterocycle aromatic group.

According to the compound of claim 1, it is characterized in that 2, Ar is identical with Ar ', is selected from C _6-20Aryl, the C of replacement _6-20Aryl, C _6-20Fused ring aryl, C _4-20Heterocyclic aryl or C _4-20The fused heterocycle aromatic group.

According to the compound of claim 1, it is characterized in that 3, Ar is different with Ar ', independently be selected from C respectively _6-20Aryl, the C of replacement _6-20Aryl, C _6-20Fused ring aryl, C _4-20Heterocyclic aryl or C _4-20The fused heterocycle aromatic group.

4, compound according to claim 1, it is characterized in that Ar and Ar ' independently are selected from phenyl, xenyl, naphthyl, anthryl, pyrenyl, fluorenyl, naphthacenyl, pyridyl, quinolyl, benzothienyl, cumarone, indyl, benzimidazolyl-, benzothiazolyl respectively.

5, compound according to claim 1 is characterized in that, Ar and Ar ' independently are selected from the phenyl to tert-butyl-phenyl, 2,4 difluorobenzene base or 4-(N, N-dimethyl amido) respectively.

6, the application of the described compound of claim 1 in organic electroluminescence device is characterized in that as luminescent material or electric transmission and hole barrier materials.

7, a kind of organic electroluminescence device comprises first electrode and second electrode, and the organic function layer between two electrodes, it is characterized in that, the one deck at least in the organic function layer comprises the compound with following structural:

Wherein n is the integer of 1-4, and Ar and Ar ' are independently selected from C respectively _6-20Aryl, the C of replacement _6-20Aryl, C _6-20Fused ring aryl, C _4-20Heterocyclic aryl or C _4-20The fused heterocycle aromatic group.

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