CN104497013A - Aza carbazole OLED (organic light emitting diode) material as well as preparation method and application thereof - Google Patents

Aza carbazole OLED (organic light emitting diode) material as well as preparation method and application thereof Download PDF

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CN104497013A
CN104497013A CN201410763903.5A CN201410763903A CN104497013A CN 104497013 A CN104497013 A CN 104497013A CN 201410763903 A CN201410763903 A CN 201410763903A CN 104497013 A CN104497013 A CN 104497013A
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CN104497013B (en
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曹建华
华瑞茂
王士波
贾磊磊
黄红亮
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Abstract

The invention discloses an aza carbazole OLED (organic light emitting diode) material as well as a preparation method and application thereof. A general structural formula of the aza carbazole OLED material is shown in a formula I as shown in the description. The OLED material has the advantages that carrier transmission efficiency can be improved, and luminous efficiency of a device can also be improved; substituent groups R1 and R2 are introduced in a compound molecule, HOMO (highest occupied molecular orbit) value of an OLED material molecule, molecular stability and glass transition temperature of a material are improved, injection of a hole is facilitated, and the OLED material is excellent in performance; and a synthesis route of the OLED material is simple and easy to operate, reaction yield is high, preparation cost of the OLED material can be reduced, and an industrial prospect is good.

Description

Azepine carbazoles OLED material and preparation method thereof and application
Technical field
The invention belongs to ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field, relate to a kind of azepine carbazoles OLED material and preparation method thereof and application.
Background technology
First organic electroluminescent (being called for short OLED) and relevant research have found the electro optical phenomenon of organic compound single-crystal anthracene as far back as people such as pope in 1963.A kind of amorphous membranous type device has been made by the method for evaporation organic molecule by the Kodak of the U.S. in 1987, has been dropped within 20V by driving voltage.This kind of device owing to having ultra-thin, all solidstate, luminous, brightness is high, visual angle is wide, fast response time, driving voltage are low, power consumption is little, bright in luster, contrast gradient is high, technological process is simple, good temp characteristic, can realize the advantages such as soft display, flat-panel monitor and area source can be widely used in, therefore obtain and study widely, develop and use.
Organic electroluminescent is mainly divided into fluorescence and phosphorescence, but according to spin quantum statistical theory, the probability of singlet excitons and triplet exciton is 1:3, and the theoretical limit namely carrying out the fluorescence of white singlet excitons radiative transition is 25, and the theoretical limit of the fluorescence of triplet exciton radiative transition is 75.The energy of the triplet excitons of 75% how is utilized to become the task of top priority.Forrest in 1997 etc. find that electrophosphorescence phenomenon breaches the restriction of electroluminescent organic material quantum yield 25% efficiency, cause people to the extensive concern of metal complexes phosphor material.From then on, people carry out large quantifier elimination to phosphor material.
Summary of the invention
The object of this invention is to provide a kind of azepine carbazoles OLED material and preparation method thereof and application.
Azepine carbazoles OLED material provided by the invention, its general structure such as formula shown in I,
In described formula I, R 1and R 2be selected from following group a or b:
Any one in the heterocyclic radical of the polycyclic aromatic vinyl of the aromatic ethylene base of a, the aromatic base being selected from C2-C60, C2-C60, the polycyclic aromatic base of C2-C60, C2-C60, the aryl amine of C2-C60, the condensed ring radical of the nitrogen atom of C2-C60, the sulfur-bearing of C6-C60 or the condensed ring radical of Sauerstoffatom, the phosphorous of C6-C60 or the condensed ring radical of silicon or boron atom and the nitrogen atom of C2-C60;
B, containing substituent group a;
In described group b, substituting group is selected from least one in hydrogen, deuterium, the aliphatic group of C1-C20, halogen and cyano group;
N is 1,2,3,4 or 5.
Concrete, in described formula I, R 1and R 2all be selected from following group any one:
In above-mentioned group, described A, B and C independently be carbon atom or nitrogen-atoms, but A, B and C can not be nitrogen-atoms simultaneously; represent substituent position;
R 3, R 4and R 5be selected from the heterocyclic radical of hydrogen, the aliphatic group of C1-C18, the aromatic base of C2-C60, the aromatic ethylene base of C2-C60, the polycyclic aromatic base of C2-C60, the polycyclic aromatic vinyl of C2-C60, the aryl amine of C2-C60, the condensed ring radical of the nitrogen atom of C2-C60 and the nitrogen atom of C2-C60 any one;
R 6be selected from the polycyclic aromatic base of the aliphatic hydrocarbon of C1-C18, the aromatic base of C2-C60 and C2-C60 any one.
Concrete, compound shown in described formula I is any one in following compound:
Shown in preparation formula I provided by the invention, the method for compound, comprises the steps:
1) by R 2-CHO and tryptamines mix in solvent, are added dropwise to trifluoroacetic acid and carry out condensation addition reaction, react complete and obtain
2) by step 1) gained after mixing in solvent carry out dehydrogenation oxidation reaction with palladium/charcoal, obtain
3) by step 2) gained mix with catalyzer, phosphorus part and alkali and carry out linked reaction, obtain compound shown in described formula I;
Described step 1)-3) in, the R in each reaction materil structure general formula 1, R 2all identical with the definition in previously described formula I with the definition of n.
The step 1 of aforesaid method) in, described R 2the mole dosage that feeds intake of-CHO, tryptamines and trifluoroacetic acid is 1.0:1.0-1.5:1.0-1.5, is specially 1.0:1.0:1.0; In described condensation addition reaction step, temperature is 0-40 DEG C, and the time is 8-16 hour, is specially 12 hours;
Described step 2) in, be 1.0:0.01-1.0 with the mass ratio of palladium/charcoal, be specially 1.0:0.02; In described dehydrogenation oxidation reactions steps, temperature is 120-140 DEG C, and the time is 12-48 hour, is specially 24 hours;
Described step 3) in, catalyzer is palladium or Pd (PPh 3) 4, Pd (PPh 3) 2cl 2, Pd 2(dba) 3or Pd (dba) 2;
Part be tri-butyl phosphine, triphenyl phosphorus, 2-dicyclohexylphosphontetrafluoroborate-2 ', 6 '-dimethoxy-biphenyl or thricyclohexyl phosphorus;
Alkali is salt of wormwood, sodium carbonate, potassium acetate, sodium tert-butoxide, cesium carbonate, potassium tert.-butoxide or sodium acetate;
Described compare for 2.0-2.5:1.0:0.005-0.02:0.01-0.05:2.0-3.0 with the mole dosage that feeds intake of catalyzer, phosphorus part and alkali, be specially 2.2:1.0:0.01:0.04:2.5,2.25:1.0:0.01:0.04:2.5,2.2-2.25:1.0:0.01:0.04:2.5,3.1:1.0:0.01:0.04:2.5,2.25-3.1:1.0:0.01:0.04:2.5 or 2.2-3.1:1.0:0.01:0.04:2.5;
In described linked reaction step, the time is 12-56 hour, is specially 24 hours;
Described step 1)-3) carry out all in an inert atmosphere; Described inert atmosphere is specially nitrogen or argon gas atmosphere;
Described step 1)-3) in, described solvent is all selected from least one in methylene dichloride, N-Methyl pyrrolidone, tetrahydrofuran (THF), toluene, DMF and dimethylbenzene.
In addition, compound shown in the formula I that the invention described above provides, at the application prepared in electroluminescent device and the electroluminescent device containing compound shown in formula I, also belongs to protection scope of the present invention.Wherein, in described electroluminescent device, compound shown in formula I is the material forming organic luminous layer;
Described electroluminescent device is specially the device of following structure:
Described electroluminescent device is made up of transparent substrate, anode layer, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively;
Wherein, the material forming described transparent substrate is glass or flexible substrate;
The material forming described anode layer is inorganic materials or organic conductive polymer; Wherein, described inorganic materials is tin indium oxide, zinc oxide, zinc tin oxide, gold and silver or copper; Described organic conductive polymer is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material forming described hole injection layer is BNP;
The material forming described hole transmission layer is TAPC;
The structural formula of described BNP and TAPC is as follows:
Form the mixture of material for being made up of compound shown in aforementioned formula I provided by the invention and phosphor material of described organic luminous layer; The mass ratio of compound and phosphor material shown in described formula I is 1:0.001-0.2, specifically can be 1:0.08;
Described phosphor material is FIrCzpic, Ir (2FLS) (acac) or Ir (dhpiq) (acac);
Wherein, the structural formula of FIrCzpic is as follows:
The structural formula of Ir (2FLS) (acac) is as follows:
The structural formula of Ir (dhpiq) (acac) is as follows:
The material forming described electron transfer layer is Alq3, Gaq3 or TPBI;
Wherein, the structural formula of Alq3, TPBI and Gaq3 is as follows successively:
The material forming described cathode layer is selected from any one or any alloys of two kinds of compositions in following element or the fluorochemical of following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
The thickness of described hole injection layer is 5-15nm, is specially 10nm;
The thickness of described hole transmission layer is 5-15nm, is specially 10nm;
The thickness of described organic luminous layer is 10-100nm, specifically can be 80nm;
The thickness of described electron transfer layer is 40nm-60nm, specifically can be 50nm;
The thickness of described cathode layer is 90nm-110nm, specifically can be 100nm.
The invention provides a kind of OLED material comprising carbazole structure unit.This OLED material not only can improve carrier transport efficiency, can also improve the luminous efficiency of device.R in compound molecule 1, R 2substituent introducing, reduces the HOMO value of this OLED material molecule, improves the stability of molecule and the second-order transition temperature of material, is more conducive to the injection in hole, is a kind of OLED material of excellent performance.The synthetic route of this material is simple to operation, and reaction yield is higher, can reduce the preparation cost of OLED material, has good industrial prospect.This OLED material can be used in any one deck in hole injection layer in organic electroluminescent LED, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, or is used in organic electroluminescence device as the hotchpotch of luminescent layer or material of main part.Use organic electroluminescent LED prepared by this OLED material, can realize the effect of high brightness, high-level efficiency, low voltage, can effectively avoid screen dim spot, performance is more excellent.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
The Performance Detection condition of embodiment 4 and 5 obtained device OD-1 to OD-5 is as follows:
Brightness and tristimulus coordinates: use spectrum scanner PhotoResearch PR-715 test;
Current density and a bright voltage: use digital sourcemeter Keithley 2420 to test;
Power efficiency: use NEWPORT 1931-C test.
The synthesis of embodiment 1, compd B H-5
Step 1: the synthesis of compound 9-(3-bromophenyl)-9H-carbazole
The N of the m-dibromobenzene of 20g (84.7mmol), the carbazole of 14g (84.7mmol), 1.6g (8.47mmol) cuprous iodide, 1.5g (16.9mmol) is dropped in 500mL reaction flask 1, N 2-dimethyl-1，2-diaminoethane, 117g (0.847mol) alkali salt of wormwood and 300ml solvent xylene, nitrogen protection is heated to 120 DEG C, insulation reaction 24 hours.Water-bath is cooled to 80 DEG C, filtered while hot, and filter cake toluene is washed, and filtrate reduced in volume is done, and resistates crosses silica column purification, and sherwood oil/eluent methylene chloride obtains white solid product 22.6g.Yield: 83%.
Step 2: the synthesis of compound 3-(9H-carbazole) phenyl aldehyde
To in 500mL reaction flask, drop into 20g (62.11mmol) step 1 product 9-(3-bromophenyl)-9H-carbazole, 300ml tetrahydrofuran (THF), nitrogen protection, cryostat, cools to-78 DEG C, be added dropwise to 27ml (2.5M, 67.5mmol) lithium hexane solution, insulation reaction 30 minutes, be added dropwise to 4.9g (67.5mmol) N, the solution of dinethylformamide and 5ml tetrahydrofuran (THF), insulation reaction 30 minutes, slowly be raised to room temperature, add the 2N diluted hydrochloric acid aqueous solution cancellation reaction of 20ml, add the ethyl acetate of 100ml, stir separatory, aqueous phase 50ml extraction into ethyl acetate 2 times, merge organic phase, cross silicagel column, sherwood oil/eluent methylene chloride obtains white solid product.Yield: 88%.
Step 3: the compound 1-(synthesis of 3-(9H-carbazole-9-base) phenyl-2,3,4,9-tetrahydrochysene-1H-piperidines also [3,4-b] indoles
To in 500mL reaction flask, 6.27g (55mmol) trifluoroacetic acid is added dropwise under dropping into 15g (55mmol) step 2 product 3-(9H-carbazole) phenyl aldehyde, 8.8g (55mmol) tryptamines, the methylene dichloride of 250ml, room temperature, stirring reaction is after 8 hours, reaction system is poured in the beaker filling 250ml frozen water and 3g sodium hydroxide, stir separatory, aqueous phase 20mL dichloromethane extraction 2 times, merge organic phase, cross silicagel column, sherwood oil/eluent methylene chloride obtains white solid product.Yield: 92%.
Step 4: the compound 1-(synthesis of 3-(9H-carbazole-9-base) phenyl-9H-pyrido [3,4-b] indoles
To in 500mL reaction flask, drop into 12.5g (30mmol) step 3 product 1-(3-(9H-carbazole-9-base) phenyl-2, 3, 4, 9-tetrahydrochysene-1H-piperidines also [3, 4-b] indoles, 2.5g 10% palladium/charcoal, the dimethylbenzene of 250ml, after stirring temperature rising reflux reacts 24 hours, cool to room temperature, filter, filter cake is returned in reaction flask, add 200ml tetrahydrofuran (THF) and 200ml methylene dichloride, stir temperature rising reflux 2 hours, cool to room temperature, filter, filtrate reduced in volume is done, add 20ml ethyl acetate to filter, filter cake ethyl acetate is washed, dry pale solid.Yield: 65%.
Step 5: the synthesis of compd B H-5
To in 250mL reaction flask, drop into 5g (12.2mmol) step 4 product 1-(3-(9H-carbazole-9-base) phenyl-9H-pyrido [3, 4-b] indoles, diiodo-benzene between 1.6g (4.8mmol), the toluene of 80ml, 44mg (0.048mmol) three (dibenzalacetone) two palladium, the 2-dicyclohexylphosphontetrafluoroborate-2 of 39mg (0.096mmol) ', 6 '-dimethoxy-biphenyl, 1.2g (12.5mmol) sodium tert-butoxide, under nitrogen protection, stirring was warming up to 100 DEG C of reactions after 24 hours, cool to room temperature, add 50ml water and stir 30 minutes, separate organic phase, aqueous phase 100ml dichloromethane extraction three times, merge organic pressure of subtracting each other concentrated dry, residue over silica gel column separating purification, with methylene dichloride/sherwood oil wash-out, obtain yellow solid.Yield: 55%.
Structure and the performance test results of this product are as follows:
(1) 1H NMR(CDCl 3,300MHz)：δ＝8.16-8.18(m,2H),7.80-7.83(m,4H),7.47-7.53(m,6H),7.42-7.44(m,6H),7.29-7.33(m,12H),7.23-7.26(m,10H)。As from the foregoing, this yellow solid product structure is correct, is compd B H-5.
(2) second-order transition temperature Tg:>300 DEG C;
(3) uv-absorbing wavelength: 295nm, 325nm, 338nm;
(4) fluorescence emission wavelengths: 415nm.
The synthesis of embodiment 2, compd B H-28
Step 1: the synthesis of compound 1-(1-naphthyl)-2,3,4,9-tetrahydrochysene-1H-piperidines also [3,4-b] indoles
According to the step of embodiment 1, only by step 3) in 3-used (9H-carbazole) phenyl aldehyde replace with 1-naphthaldehyde, obtain target compound 1-(1-naphthyl)-2,3,4,9-tetrahydrochysene-1H-piperidines also [3,4-b] indoles, white solid, yield: 94%.
Step 2: the synthesis of compound 1-(1-naphthyl)-9H-pyrido [3,4-b] indoles
According to the step of embodiment 1, only by step 4) in 1-used (3-(9H-carbazole-9-base) phenyl-2,3,4,9-tetrahydrochysene-1H-piperidines also [3,4-b] indoles replaces with 1-(1-naphthyl)-2,3,4,9-tetrahydrochysene-1H-piperidines also [3,4-b] indoles, obtain target compound 1-(1-naphthyl)-9H-pyrido [3,4-b] indoles, yellow crystals, yield: 74%.
Step 3: the synthesis of compd B H-28
According to the step of embodiment 1, by step 5) in 1-used (3-(9H-carbazole-9-base) phenyl-9H-pyrido [3,4-b] indoles replaces with 1-(1-naphthyl)-9H-pyrido [3,4-b] indoles, between inciting somebody to action, diiodo-benzene replaces with 4,4 '-diiodobiphenyl, obtains target compound, yellow powder, yield: 62%.
Structure and the performance test results of this product are as follows:
(1) 1H NMR(CDCl 3,300MHz)：δ＝8.16-8.18(m,2H),7.82-7.85(m,6H),7.47-7.49(m,4H),7.44-7.47(m,6H),7.32-7.38(m,10H),7.23-7.25(m,4H)。As from the foregoing, this yellow solid product structure is correct, is compd B H-28.
(2) second-order transition temperature Tg:278 DEG C;
(3) uv-absorbing wavelength: 315nm, 325nm;
(4) fluorescence emission wavelengths: 410nm.
The synthesis of embodiment 3, compd B H-61
Step 1: compound N, the synthesis of N-phenylbenzene-4-(2,3,4,9-tetrahydrochysene-1H-piperidines is [3,4-b] indoles-1-base also) amine
According to the step of embodiment 1, only by step 3) in 3-used (9H-carbazole) phenyl aldehyde replace with 4-pentanoic benzaldehyde, obtain target compound N, N-phenylbenzene-4-(2,3,4,9-tetrahydrochysene-1H-piperidines also [3,4-b] indoles-1-base) amine, white solid, yield: 89%.
Step 2: compound N, the synthesis of N-phenylbenzene-4-(9H-pyrido [3,4-b] indoles-1-base) amine
According to the step of embodiment 1, only by step 4) in 1-used (3-(9H-carbazole-9-base) phenyl-2,3,4,9-tetrahydrochysene-1H-piperidines also [3,4-b] indoles replaces with N, N-phenylbenzene-4-(2,3,4,9-tetrahydrochysene-1H-piperidines is [3,4-b] indoles-1-base also) amine, obtain target compound N, N-phenylbenzene-4-(9H-pyrido [3,4-b] indoles-1-base) amine, yellow crystals, yield: 76%.
Step 3: the synthesis of compd B H-61
To in 250mL reaction flask, drop into 5g (12.15mmol) step 2 product N, N-phenylbenzene-4-(9H-pyrido [3, 4-b] indoles-1-base) amine, 6.5g (14.5mmol) 9-(4 '-iodo-[1, 1 '-biphenyl]-4-base)-9H-carbazole, the toluene of 80ml, 110mg (0.12mmol) three (dibenzalacetone) two palladium, the 2-dicyclohexylphosphontetrafluoroborate-2 of 98.5mg (0.24mmol) ', 6 '-dimethoxy-biphenyl, 1.75g (18.2mmol) sodium tert-butoxide, under nitrogen protection, stirring was warming up to 100 DEG C of reactions after 24 hours, cool to room temperature, add 50ml water and stir 30 minutes, separate organic phase, aqueous phase 100ml dichloromethane extraction three times, merge organic pressure of subtracting each other concentrated dry, residue over silica gel column separating purification, with methylene dichloride/sherwood oil wash-out, obtain yellow solid.Yield: 62%.
Structure and the performance test results of this product are as follows:
(1) 1H NMR(CDCl 3,300MHz)：δ＝8.15-8.18(m,3H),7.82-7.83(m,1H),7.52-7.55(m,4H),7.44-7.46(m,2H),7.22-7.28(m,14H),7.06-7.10(m,12H)。As from the foregoing, this yellow solid product structure is correct, is compd B H-61.
(2) second-order transition temperature Tg:227 DEG C;
(3) uv-absorbing wavelength: 325nm, 338nm;
(4) fluorescence emission wavelengths: 402nm.
As can be seen from above-described embodiment 1 ~ 3, provided by the invention have compound shown in formula I, has very high second-order transition temperature, and preferably carrier transport ability and luminous power, therefore has a good application prospect in OLED field.On the preparation process basis of above-mentioned eight embodiments, reactant consumption expanded on year-on-year basis or reduces, all not affecting the quality of gained OLED material.
Embodiment 4, prepare electroluminescent device OD-1, OD-2, OD-3
1) the glass substrate supersound process 30 minutes in clean-out system will ITO conductive layer being coated with, rinse in deionized water, in acetone/ethanol mixed solvent ultrasonic 30 minutes, be baked to complete drying under a clean environment, 10 minutes are irradiated with ultraviolet rays cleaning machine, and with low energy positively charged ion bundle bombarded surface.
2) the above-mentioned ito glass substrate handled well is placed in vacuum chamber, is evacuated to 1 × 10 -5~ 9 × 10 -3pa, above-mentioned anode tunic continues successively that evaporation compd B NP is as hole injection layer, and TAPC is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 10nm;
Wherein, the structural formula of BNP and TAPC is as follows:
3) on hole transmission layer, continue the organic luminous layer of mixture as device of compd B H-5 shown in evaporation one deck embodiment 1 gained formula I and phosphor material FIrCzpic composition, evaporation rate is 0.1nm/s, and evaporation thickness is 80nm; Wherein, FIrCzpic is 8% of BH-5 quality;
Wherein, the structural formula of FIrCzpic is as follows:
4) on organic luminous layer, continue the electron transfer layer of evaporation one deck TPBI material as device, evaporation rate is 0.1nm/s, and evaporation thickness is 50nm;
Wherein, the structural formula of TPBI is as follows:
5) on electron transfer layer successively evaporation magnesium/ag alloy layer as the cathode layer of device, wherein the evaporation rate of magnesium/ag alloy layer is 2.0 ~ 3.0nm/s, evaporation thickness is 100nm, and the mass ratio of magnesium and silver is 1:9, obtains device OD-1 provided by the invention.
According to upper identical step, by step 3) BH-5 used replaces with the H-51 of compd B shown in formula I phosphor material FIrCzpic is replaced with Ir (2FLS) (acac) and obtain device OD-2 provided by the invention;
Wherein, the structural formula of Ir (2FLS) (acac) is as follows:
According to upper identical step, by step 3) BH-5 used replaces with the H-65 of compd B shown in formula I phosphor material FIrCzpic is replaced with Ir (dhpiq) (acac) and obtain device OD-3 provided by the invention;
Wherein, the structural formula of Ir (dhpiq) (acac) is as follows:
Reference examples 1, fabricate devices OD-4 and OD-5
According to the step of embodiment 5, only by step 3) BH-5 used replaces with mCP or CBP, obtains device OD-4 and OD-5.
Wherein, the structural formula of mCP and CBP is as follows:
The performance test results of obtained device OD-1 to OD-5 is as shown in table 1.
The performance test results of table 1, OD-1 to OD-5
As from the foregoing, under the condition that device architecture is identical, use material formula I of the present invention as material of main part, the device that the phosphor material adulterating 8% ratio prepares is compared as material of main part with mCP with CBP, luminous power efficiency and quantum yield obviously want high, and performance is more excellent.

Claims (10)

1. compound shown in formula I,
In described formula I, R 1and R 2be selected from following group a or b:
Any one in the heterocyclic radical of the polycyclic aromatic vinyl of the aromatic ethylene base of a, the aromatic base being selected from C2-C60, C2-C60, the polycyclic aromatic base of C2-C60, C2-C60, the aryl amine of C2-C60, the condensed ring radical of the nitrogen atom of C2-C60, the sulfur-bearing of C6-C60 or the condensed ring radical of Sauerstoffatom, the phosphorous of C6-C60 or the condensed ring radical of silicon or boron atom and the nitrogen atom of C2-C60;
B, containing substituent group a;
In described group b, substituting group is selected from least one in hydrogen, deuterium, the aliphatic group of C1-C20, halogen and cyano group;
N is 1,2,3,4 or 5.
2. compound according to claim 1, is characterized in that: in described formula I, R 1and R 2all be selected from following group any one:
In above-mentioned group, described A, B and C independently be carbon atom or nitrogen-atoms, but A, B and C can not be nitrogen-atoms simultaneously; represent substituent position;
R 3, R 4and R 5be selected from the heterocyclic radical of hydrogen, the aliphatic group of C1-C18, the aromatic base of C2-C60, the aromatic ethylene base of C2-C60, the polycyclic aromatic base of C2-C60, the polycyclic aromatic vinyl of C2-C60, the aryl amine of C2-C60, the condensed ring radical of the nitrogen atom of C2-C60 and the nitrogen atom of C2-C60 any one;
R 6be selected from the polycyclic aromatic base of the aliphatic hydrocarbon of C1-C18, the aromatic base of C2-C60 and C2-C60 any one.
3., according to the arbitrary described compound of claim 1-2, it is characterized in that: compound shown in described formula I is any one in following compound:
4. prepare a method for compound shown in arbitrary described formula I in claim 1-3, comprise the steps:
1) by R 2-CHO and tryptamines mix in solvent, then add trifluoroacetic acid and carry out condensation addition reaction, react complete and obtain
2) by step 1) gained after mixing in solvent carry out dehydrogenation oxidation reaction with palladium/charcoal, obtain
3) by step 2) gained mix with catalyzer, phosphorus part and alkali and carry out linked reaction, obtain compound shown in described formula I;
Described step 1)-3) in, the R in each reaction materil structure general formula 1, R 2all identical with the definition in formula I described in claim 1 with the definition of n.
5. method according to claim 4, is characterized in that: described step 1) in, R 2the mole dosage that feeds intake of-CHO, tryptamines and trifluoroacetic acid is 1.0:1.0-1.5:1.0-1.5; In described condensation addition reaction step, temperature is 0-40 DEG C, and the time is 8-16 hour;
Described step 2) in, be 1.0:0.01-1.0 with the mass ratio of palladium/charcoal; In described dehydrogenation oxidation reactions steps, temperature is 120-140 DEG C, and the time is 12-48 hour;
Described step 3) in, described catalyzer is palladium, Pd (PPh 3) 4, Pd (PPh 3) 2cl 2, Pd 2(dba) 3or Pd (dba) 2;
Described phosphorus part be tri-butyl phosphine, triphenyl phosphorus, 2-dicyclohexylphosphontetrafluoroborate-2 ', 6 '-dimethoxy-biphenyl or thricyclohexyl phosphorus;
Described alkali is salt of wormwood, sodium carbonate, potassium acetate, sodium tert-butoxide, cesium carbonate, potassium tert.-butoxide or sodium acetate;
Described the mole dosage ratio that feeds intake of catalyzer, phosphorus part and alkali is 2.0-2.5:1.0:0.005-0.02:0.01-0.05:2.0-3.0;
In described linked reaction step, the time is 12-56 hour;
Described step 1)-3) carry out all in an inert atmosphere;
Described step 1)-3) in, described solvent is all selected from least one in methylene dichloride, N-Methyl pyrrolidone, tetrahydrofuran (THF), toluene, DMF and dimethylbenzene.
6. shown in the arbitrary described formula I of claim 1-3, compound is preparing the application in electroluminescent device.
7. the electroluminescent device containing compound shown in the arbitrary described formula I of claim 1-3.
8. application according to claim 6 or device according to claim 7, is characterized in that: in described electroluminescent device, and compound shown in formula I is the material forming organic luminous layer.
9. application according to claim 8 or device according to claim 8, is characterized in that: described electroluminescent device is made up of transparent substrate, anode layer, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively;
Wherein, the material forming described transparent substrate is glass or flexible substrate;
The material forming described anode layer is inorganic materials or organic conductive polymer; Wherein, described inorganic materials is tin indium oxide, zinc oxide, zinc tin oxide, gold and silver or copper; Described organic conductive polymer is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material forming described hole injection layer is BNP;
The material forming described hole transmission layer is TAPC;
The structural formula of described BNP and TAPC is as follows:
Form the mixture of material for being made up of compound shown in the arbitrary described formula I of claim 1-3 and phosphor material of described organic luminous layer; The mass ratio of compound and phosphor material shown in described formula I is 1:0.001-0.2;
Described phosphor material is FIrCzpic, Ir (2FLS) (acac) or Ir (dhpiq) (acac);
Wherein, the structural formula of FIrCzpic is as follows:
The structural formula of Ir (2FLS) (acac) is as follows:
The structural formula of Ir (dhpiq) (acac) is as follows:
The material forming described electron transfer layer is Alq3, Gaq3 or TPBI;
Wherein, the structural formula of Alq3, TPBI and Gaq3 is as follows successively:
The material forming described cathode layer is selected from any one or any alloys of two kinds of compositions in following element or the fluorochemical of following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
10. application according to claim 9 or device according to claim 9, is characterized in that:
The thickness of described hole injection layer is 5nm-15nm;
The thickness of described hole transmission layer is 5nm-15nm;
The thickness of described organic luminous layer is 10nm-100nm;
The thickness of described electron transfer layer is 40nm-60nm;
The thickness of described cathode layer is 90nm-110nm.
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