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CN103936653A - Benzo carbazoles OLED material, its preparation method and its application - Google Patents

Benzo carbazoles OLED material, its preparation method and its application Download PDF

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Publication number
CN103936653A
CN103936653A CN201310680508.6A CN201310680508A CN103936653A CN 103936653 A CN103936653 A CN 103936653A CN 201310680508 A CN201310680508 A CN 201310680508A CN 103936653 A CN103936653 A CN 103936653A
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formula
aromatic
groups
condensed ring
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曹建华
郭剑
李雅敏
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Abstract

The invention discloses a benzo carbazoles OLED material, its preparation method and its application. A structural general formula of the benzo carbazoles OLED material is disclosed as a formula (I). The OLED material can increase the carrier transmission efficiency and enhance the luminescence efficiency of a device. Introduction of R1 and R2 substituents in the compound molecule is capable of reducing HOMO value of the OLED material molecule, and is capable of increasing the molecule stability and material glass transition temperature, and is in favor of cavity injection, the invention provides the OLED material with excellent performance. The preparation method has the advantages of simple synthesis route, easy operation, high reaction yield, and reduced preparation cost of the OLED material, and the preparation method has good industrial prospect.

Description

Benzocarbazole OLED material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic electroluminescence display, and relates to a benzocarbazole OLED material, and a preparation method and application thereof.
Background
Organic electroluminescence (abbreviated as OLED) and related research firstly discovered the electroluminescence phenomenon of organic compound single crystal anthracene in pope et al as early as 1963. Kodak company of the United states of 1987 made an amorphous film device by evaporating small organic molecules, and reduced the driving voltage to within 20V. The device has the advantages of ultra-light weight, full curing, self luminescence, high brightness, wide viewing angle, high response speed, low driving voltage, low power consumption, bright color, high contrast, simple process, good temperature characteristic, soft display and the like, and can be widely applied to flat panel displays and surface light sources, so the device is widely researched, developed and used.
Organic electroluminescence is largely divided into fluorescence and phosphorescence, but according to the spin quantum statistical theory, the probability of singlet excitons and triplet excitons is 1:3, i.e., the theoretical limit of fluorescence from radiative transition of singlet excitons is 25, and the theoretical limit of fluorescence from radiative transition of triplet excitons is 75. It is urgent to use 75% of the energy of triplet excitons. Forrest et al discovered in 1997 that the phosphorescence electroluminescence phenomenon breaks through the limit of 25% efficiency of the quantum efficiency of the organic electroluminescence material, and arouses people to pay extensive attention to the metal complex phosphorescence material. Since then, much research has been conducted on phosphorescent materials.
Disclosure of Invention
The invention aims to provide a benzocarbazole OLED material and a preparation method and application thereof.
The benzocarbazole OLED material provided by the invention has a structural general formula shown in a formula I,
in the formula I, R1Selected from the following groups a or b:
a. any one selected from an aromatic group of C2-C60, an aromatic vinyl group of C2-C60, a condensed ring aromatic group of C2-C60, a condensed ring aromatic vinyl group of C2-C60, an aromatic amine group of C2-C60, a nitrogen atom-containing condensed ring group of C2-C60, a sulfur or oxygen atom-containing condensed ring group of C6-C60, and a nitrogen atom-containing heterocyclic group of C2-C60;
b. a substituent-containing group a;
R2selected from the following groups c or d:
c. any one selected from hydrogen, halogen, methyl, methoxy, aromatic group of C2-C60, aromatic vinyl group of C2-C60, condensed ring aromatic group of C2-C60, condensed ring aromatic vinyl group of C2-C60, aromatic amine group of C2-C60, condensed ring group of C2-C60 containing nitrogen atom, condensed ring group of C6-C60 containing phosphorus or silicon or boron atom and heterocyclic group of C2-C60 containing nitrogen atom;
d. a substituent-containing group c;
in the group b and the group d, the substituent is at least one selected from deuterium, C1-C20 aliphatic hydrocarbon group, halogen and cyano;
n is an integer of 1 to 5.
Preferably, in the formula I, R1、R2Are all selected from any one of the following groups:
in the above groups, A, B and C are each independently a carbon atom or a nitrogen atom, but A, B and C cannot be both nitrogen atoms,represents the position of a substituent;
R3any one selected from hydrogen, an aromatic group of C2-C60, an aromatic vinyl group of C2-C60, a condensed ring aromatic group of C2-C60, a condensed ring aromatic vinyl group of C2-C60, an aromatic amine group of C2-C60, a condensed ring group of C2-C60 containing a nitrogen atom, and a heterocyclic group of C2-C60 containing a nitrogen atom;
R4and R5Any one of aliphatic hydrocarbon groups of C1-C18, aromatic groups of C2-C60, condensed ring aromatic groups of C2-C60, aromatic amine groups of C2-C60, aromatic groups of C2-C60 connected with heterocycle and aromatic groups of C2-C60 connected with alkyl groups of C1-C18;
R6any one selected from aliphatic hydrocarbon groups of C1-C18, aromatic groups of C2-C60 and condensed ring aromatic groups of C2-C60;
R7any one selected from hydrogen, aliphatic hydrocarbon groups of C1-C18, aromatic groups of C2-C60, aromatic vinyl groups of C2-C60, fused ring aromatic groups of C2-C60 and fused ring aromatic vinyl groups of C2-C60;
d and E independently represent any one of an aromatic group of C2-C60, an aromatic vinyl group of C2-C60, a condensed ring aromatic group of C2-C60, a condensed ring aromatic vinyl group of C2-C60, a condensed ring group of C2-C60 and a heterocyclic group of C2-C60 containing a nitrogen atom;
f and G each independently represent a carbon atom or a nitrogen atom.
Specifically, the compound shown in the formula I is any one of the following compounds:
the invention provides a method for preparing a compound shown as a formula I, which comprises the following steps:
1) will be provided withUniformly mixing the catalyst, the ligand and the alkali in a solvent for ring closing reaction to obtain the catalyst
2) Subjecting the product obtained in step 1)Mixing with potassium scrap in solvent, coupling reacting, quenching reaction with mixed solution of tetrahydrofuran and water to obtain final product
3) Subjecting the product obtained in step 2)Uniformly mixing the compound with a catalyst, a phosphorus ligand and alkali, refluxing and reacting to obtain a compound shown in the formula I;
in the steps 1) to 3), R in the structural general formula of each reactant1、R2And n are as defined above for formula I.
In step 1) of the above process, the catalyst is palladium acetate or Pd (PPh)3)4、Pd(PPh3)2Cl2Or Pd (dba)2；
The ligand is tri-tert-butylphosphine, triphenylphosphine or tricyclohexylphosphine;
the alkali is potassium carbonate, sodium carbonate, potassium acetate or sodium acetate;
the above-mentionedThe feeding molar usage of the catalyst, the ligand and the alkali is 1.0: 1.0-1.5: 0.01-0.05: 0.02-0.10: 2.0-3.0, specifically 1.0: 1.2: 0.02: 0.05: 2.5;
in the ring-closing reaction, the temperature is 100-150 ℃, and the time is 8-16 hours, specifically 12 hours;
in the step 2) of the said step,the feeding molar amount of the potassium chips is 1.0: 1.0-5.0, specifically 1.0: 4.0;
in the mixed liquid composed of tetrahydrofuran and water, the volume ratio of tetrahydrofuran to water is 1.0: 1.0;
in the step of the coupling reaction, the temperature is room temperature, and the time is 12-48 hours, specifically 24 hours;
in the step 3), the catalyst is tris (dibenzylideneacetone) dipalladium, palladium acetate and Pd (PPh)3)4Or Pd (PPh)3)2Cl2Or Pd (dba)2；
The phosphorus ligand is 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, tri-tert-butylphosphine, triphenylphosphine or tricyclohexylphosphine;
the alkali is sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide or potassium hydroxide;
the feeding molar ratio of the catalyst to the phosphorus ligand to the alkali is 2.0-2.5: 1.0: 0.005-0.02: 0.01-0.05: 2.0-3.0, specifically 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 the reaction step, the time is 24-56 hours, specifically 48 hours;
the steps 1) to 3) are all carried out in an inert atmosphere; the inert atmosphere is specifically nitrogen or argon atmosphere;
in the steps 1) to 3), the solvent is at least one selected from N-methylpyrrolidone, tetrahydrofuran, toluene, N-dimethylformamide and xylene.
In addition, the luminescent material containing the compound shown in the formula I provided by the invention and the application of the compound shown in the formula I in preparing the luminescent material also belong to the protection scope of the invention; wherein the fluorescence emission wavelength of the luminescent material is specifically 370-420 nm. Specifically 378, 407, 414, 418, 378-414 or 407-418 nm;
the application of the compound shown in the formula I in the preparation of an electroluminescent device and the electroluminescent device containing the compound shown in the formula I also belong to the protection scope of the invention. In the electroluminescent device, the compound shown in the formula I is a material for forming an organic light-emitting layer;
the electroluminescent device may specifically have the following structure:
the organic electroluminescent device comprises a transparent substrate, an anode, a hole transport layer, an organic light emitting layer, an electron transport layer and a cathode layer from bottom to top in sequence;
wherein, the material for forming the transparent substrate is glass or a flexible substrate;
the anode layer is made of inorganic materials or organic conducting polymers; wherein the inorganic material is indium tin oxide, zinc oxide, tin oxide, gold, silver or copper; the organic conducting polymer is selected from at least one of polythiophene, sodium polyvinyl benzene sulfonate and polyaniline;
the material constituting the hole transport layer is selected from at least one of TDATA and NPB;
the structural formulas of NPB and TDATA are as follows:
the material for forming the organic light-emitting layer is a compound represented by formula I anda mixture of components; the compounds of the formula I andthe mass ratio of (1): 0.001-0.2, specifically 1: 0.08;
the material for forming the electron transport layer is Alq3, Gaq3 or BPhen;
wherein the structural formulas of Alq3, BPhen and Gaq3 are as follows in sequence:
the cathode layer is made of a material selected from any one or two of the following elements: lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold, and silver.
The thickness of the hole transport layer is 5-15nm, specifically 10 nm;
the thickness of the organic light-emitting layer is 10-100nm, specifically 80 nm;
the thickness of the electron transmission layer is 40-60nm, specifically 50 nm;
the thickness of the cathode layer is 90-110nm, specifically 100 nm.
The invention provides an OLED material containing carbazole structural units. The OLED material can improve the carrier transmission efficiency and the luminous efficiency of the device. In the compound molecule R1、R2The introduction of the substituent group reduces the HOMO value of the OLED material molecule, improves the stability of the molecule and the glass transition temperature of the material, is more beneficial to the injection of holes, and is an OLED material with excellent performance. The synthesis route of the material is simple and easy to operate, the reaction yield is high, the preparation cost of the OLED material can be reduced, and the material has a good industrial prospect. The OLED material can be used in any one of a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer in an organic electroluminescent diode, or can be used as a dopant or a host material of the light emitting layer in an organic electroluminescent device. The organic electroluminescent diode prepared by the OLED material can realize the effects of high brightness, high efficiency and low voltage, can effectively avoid screen dark spots and has more excellent performance.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The starting material tris (4-bromophenyl) amine used in example 3 below was prepared as follows:
step 1: synthesis of triphenylamine
Into a 100mL reaction flask, 5g (55mmol) of aniline, 21g (121mmol) of bromobenzene, 250mg (0.275mmol) of tris (dibenzylideneacetone) dipalladium, 450mg (1.1mmol) of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 16g (176mmol) of sodium tert-butoxide and 50mL of toluene were charged, and the mixture was refluxed under nitrogen protection and reacted for 24 hours. Adding the system into a beaker containing 100mL of water, adding 100mL of ethyl acetate, stirring, separating the liquid, extracting the aqueous phase for 2 times by using 50mL of ethyl acetate, combining the organic phases, passing through a silica gel column, and leaching by using petroleum ether/dichloromethane to obtain a white solid product. Yield: 96 percent.
Step 2: synthesis of tris (4-bromophenyl) amine
Into a 100mL reaction flask, 2.45g (10mmol) of the product of step 1, triphenylamine and 25mL of DMF were charged, and stirred to completely dissolve triphenylamine, and 5.9g (33mmol) of NBS was dissolved in 10mL of DMF in a constant pressure dropping funnel, and slowly added dropwise to the system, and stirred at room temperature overnight. Putting the system into a beaker filled with 300ml of water, fully stirring and carrying out suction filtration. White powder was extracted with ethyl acetate: ethanol =1:1 recrystallized to white crystals. Yield: 87.1 percent.
The starting material, 2, 8-dibromodibenzo [ b, d ] thiophene, used in example 4 below was prepared as follows:
into a 250mL reaction flask, 18.4(0.1mol) of dibenzo [ b, d ] was charged]Thiophene and 150ml chloroform, the system is placed in an ice-water bath to be cooled to 0 ℃ and 33.6g (0.21mol) of Br2Dissolving in 50ml chloroform in a constant pressure dropping funnel, slowly dropping into the system, naturally raising to room temperature after dropping, and stirring overnight. The system is added with 20 percent sodium thiosulfate solution to remove excessive Br2Suction filtration, washing of filter cake for 2 times, washing of sodium carbonate aqueous solution for 2 times, and recrystallization yield of chloroform: 43.9 percent.
The performance test conditions of the devices OD-1 to OD-4 obtained in examples 5 and 6 were as follows:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1 Synthesis of 1, 3-bis (9H-dibenzo [ a, c ] carbazol-9-yl) benzene
Step 1: synthesis of compound 2, 3-diphenyl indole
A500 mL reaction flask was charged with 20g (116.3 mmol) of o-bromoaniline, 24.8g (139.5mmol) of tolane, 0.52g (2.3 mmol) of palladium acetate as a catalyst, 1.3g (5.8 mmol) of ligand tri-tert-butylphosphine, 37.2g (290.3mmol) of basic potassium carbonate and 400mL of N-methylpyrrolidone (NMP) as a solvent, and heated to 110 ℃ under nitrogen protection to effect a ring-closing reaction for 12 h. BodyAdding into a beaker containing 500mL of water, adding 200mL of ethyl acetate, stirring, separating, extracting the water phase with 200mL of ethyl acetate for 2 times, washing the organic phase with 100mL of saturated salt solution for 2 times, combining the organic phases, passing through a silica gel column, and leaching with petroleum ether/dichloromethane to obtain a white solid product, namely 2, 3-diphenylindoleYield: 80 percent.
Step 2: synthesis of 9H-dibenzo [ a, c ] carbazole compound
2g (7.4mmol) of the product 2, 3-diphenylindole in the step 1, 1g (29.7mmol) of metal potassium scrap and 300mL of THF are put into a 500-mL reaction bottle and are vigorously stirred at room temperature under the protection of nitrogen to carry out coupling reaction, the system becomes purple black, and after 24 hours, 10mL of THF and H which are equal in volume are added2And the mixed solution consisting of O quenches the reaction, and the system changes from purple black to orange. THF was spin-dried under reduced pressure, 100mL of water and 100mL of ethyl acetate were added, the mixture was stirred for liquid separation, the aqueous phase was extracted 2 times with 50mL of ethyl acetate, the organic phases were combined, passed through a silica gel column and eluted with petroleum ether/dichloromethane to give a white solid product. Yield: 50 percent.
1H NMR(CDCl3300 MHz): δ =7.89-7.91(s,1H),8.84-8.88(t,2H),8.77-8.80(d,1H),8.53-8.59(t,2H),7.68-7.78(m,4H),7.55-7.57(t,1H),7.42-7.44(t,1H),7.7.37-7.39(t, 1H). As can be seen from the above, the white solid product has a correct structure and is 9H-dibenzo [ a, c ]]Carbazole
And step 3: synthesis of compound 1, 3-di (9H-dibenzo [ a, c ] carbazol-9-yl) benzene
0.2g (0.8mmol) of m-dibromobenzene, 0.47g (1.8mmol) of 9H-dibenzo [ a, c ] carbazole obtained in the step 2), 8.3mg (0.008mmol) of catalyst tris (dibenzylideneacetone) dipalladium, 13.1mg (0.032mmol) of phosphorus ligand 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 0.192g (2mmol) of alkali sodium tert-butoxide and 3mL of solvent xylene are put into a 25mL reaction bottle, the reaction system is heated and refluxed for reaction for 48 hours under the protection of nitrogen, poured into a beaker containing 50mL of water, 50mL of ethyl acetate is added, the mixture is stirred and separated, the aqueous phase is extracted for 2 times with 20mL of ethyl acetate, the organic phase is combined, and the white solid product is obtained by silica gel column and petroleum ether/dichloromethane leaching. Yield: 30 percent.
The structure and performance detection results of the product are as follows:
（1）1H NMR(CDCl3300 MHz): δ =7.89-7.91(d,2H),6.82-6.85(d,2H),5.35(b, 1H). As can be seen from the above, the white solid product has a correct structure and is the compound CJH1,1, 3-bis (9H-dibenzo [ a, c ]]Carbazol-9-yl) benzene.
(2) Glass transition temperature Tg: 227.62 deg.C;
(3) ultraviolet absorption wavelength: 295nm, 325nm, 338 nm;
(4) fluorescence emission wavelength: 418 nm.
Example 2 Synthesis of the Compound 4, 4' -bis (9H-dibenzo [ a, c ] carbazol-9-yl) biphenyl
Following the procedure of example 1, replacing only m-dibromobenzene used in step 3) with 4,4 '-dibromobiphenyl gave the target compound 4, 4' -bis (9H-dibenzo [ a, c ] carbazol-9-yl) biphenyl in yield: 25 percent.
The structure and performance detection results of the product are as follows:
（1）1H NMR(CDCl3300 MHz): δ =9.13-9.15(d,1H),8.91-9.03(m,6H), 8.69-8.74(d,1H), 6.98-8.04(m,23H), 6.68-6.73(d, 1H). As can be seen from the above, the white solid product has correct structure and is the compound CJH11,4, 4' -bis (9H-dibenzo [ a, c ]]Carbazol-9-yl) biphenyl.
(2) Glass transition temperature Tg: 265.49 deg.C;
(3) ultraviolet absorption wavelength: 295nm, 315nm, 338 nm;
(4) fluorescence emission wavelength: 378 nm.
Example 3 Synthesis of the Compound tris (4- (9H-dibenzo [ a, c ] carbazol-9-yl) phenyl) amine
Steps 1) and 2) were the same as in example 1;
3) into a 25mL reaction flask, 0.39g (0.8mmol) of tris (4-bromophenyl) amine, 0.67g (2.5mmol) of 9H-dibenzo [ a, c ] carbazole, 8.3mg (0.008mmol) of tris (dibenzylideneacetone) dipalladium, 13.1mg (0.032mmol) of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 0.307g (3.2mmol) of sodium tert-butoxide and 3mL of xylene were charged, and after reaction for 48 hours under nitrogen protection with heating and refluxing, the reaction system was poured into a beaker containing 50mL of water, and 50mL of ethyl acetate was added, followed by stirring and liquid separation, extraction of the aqueous phase with 20mL of ethyl acetate for 2 times, combination of the organic phases, passing through a silica gel column, and elution with petroleum ether/dichloromethane to obtain a white solid product. Yield: 23 percent.
The structure and performance detection results of the product are as follows:
（1）1H NMR(CDCl3300 MHz): δ =8.96-8.99(d,3H),8.81-8.85(q,6H),8.69-8.72(q,3H),7.50-7.85(m,24H),7.39-7.49(m, 12H). As can be seen from the above, the white solid product has a correct structure and is the compound CJH21, tris (4- (9H-dibenzo [ a, c ])]Carbazol-9-yl) phenyl) amine.
(2) Glass transition temperature Tg: none;
(3) ultraviolet absorption wavelength: 293nm, 328nm, 335 nm;
(4) fluorescence emission wavelength: and 407 nm.
Example 4 Synthesis of the Compound 2, 8-bis (9H-dibenzo [ a, c ] carbazol-9-yl) dibenzo [ b, d ] thiophene
Steps 1) and 2) were the same as in example 1;
3) into a 25mL reaction flask, 0.27g (0.8mmol) of 2, 8-dibromodibenzo [ b, d ] thiophene, 0.47g (1.76mmol) of 9H-dibenzo [ a, c ] carbazole, 8.3mg (0.008mmol) of tris (dibenzylideneacetone) dipalladium, 13.1mg (0.032mmol) of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 0.2g (2.0mmol) of sodium tert-butoxide and 3mL of xylene were charged, and after heating and refluxing under nitrogen protection for 48 hours, the reaction system was poured into a beaker containing 50mL of water, and 50mL of ethyl acetate was added, followed by stirring and liquid separation, extraction of the aqueous phase with 20mL of ethyl acetate for 2 times, combination of the organic phases, passing through a silica gel column, and elution with petroleum ether/dichloromethane to obtain a yellow solid product. Yield: 30 percent.
The structure and performance detection results of the product are as follows:
（1）1H NMR(CDCl3,300MHz)：δ=8.86-8.96(d,2H),8.78-8.84(q,4H),8.68-8.73(d,2H),8.28-8.34(d,2H),8.11-8.14(d,2H),7.68-7.79(m,2H),7.37-7.65(m,12H),7.157.28(m, 4H). As can be seen from the above, the yellow solid product has correct structure and is compound CJH41,2, 8-bis (9H-dibenzo [ a, c ]]Carbazol-9-yl) dibenzo [ b, d]Thiophene.
(2) Glass transition temperature Tg: 163.82 deg.C;
(3) ultraviolet absorption wavelength: 290nm, 315nm, 325 nm;
(4) fluorescence emission wavelength: 414 nm.
As can be seen from the embodiments 1 to 4, the compound shown in the formula I has high glass transition temperature, and good carrier transport capacity and light-emitting capacity, so that the compound has a good application prospect in the field of OLEDs. On the basis of the preparation process of the embodiment, the quality of the obtained OLED material is not affected by enlarging or reducing the reactant dosage in the same ratio.
Example 5 preparation of electroluminescent devices OD-1, OD-2
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, continuously and respectively evaporating a compound NPB on the anode layer film to be used as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
wherein the structural formula of NPB is as follows:
3) a further layer of the compound CJH1 of the formula I obtained in example 1 and phosphorescence was deposited on the hole-transporting layerMaterialThe formed mixture is used as an organic light-emitting layer of a device, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 80 nm; wherein FIrpic is 8% of CJH1 by mass;
4) continuously evaporating a layer of BPhen material on the organic light-emitting layer to be used as an electron transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 50 nm;
wherein, the structural formula of BPhen is as follows:
5) and sequentially evaporating a magnesium/silver alloy layer on the electron transport layer to serve as a cathode layer of the device, wherein the evaporation rate of the magnesium/silver alloy layer is 2.0-3.0 nm/s, the evaporation film thickness is 100nm, and the mass ratio of magnesium to silver is 1: and 9, obtaining the device OD-1 provided by the invention.
Following the same procedure as above, only CJH1 used in step 3) was replaced by the compound CJH11 of formula I obtained in example 2, resulting in device O-2 provided by the present invention;
comparative example 1 preparation of devices OD-3 and OD-4
Following the procedure of example 5, only CJH1 used in step 3) was replaced with mCP or CBP, resulting in devices OD-3 and OD-4.
Wherein the mCP and CBP have the following structural formulas:
the results of performance measurements of the resulting devices OD-1 to OD-4 are shown in Table 1.
TABLE 1 Performance test results of OD-1 to OD-4

Claims (9)

1. A compound of the formula I, wherein,
in the formula I, R1Selected from the following groups a or b:
a. any one selected from an aromatic group of C2-C60, an aromatic vinyl group of C2-C60, a condensed ring aromatic group of C2-C60, a condensed ring aromatic vinyl group of C2-C60, an aromatic amine group of C2-C60, a nitrogen atom-containing condensed ring group of C2-C60, a sulfur or oxygen atom-containing condensed ring group of C6-C60, and a nitrogen atom-containing heterocyclic group of C2-C60;
b. a substituent-containing group a;
R2selected from the following groups c or d:
c. any one selected from hydrogen, halogen, methyl, methoxy, aromatic group of C2-C60, aromatic vinyl group of C2-C60, condensed ring aromatic group of C2-C60, condensed ring aromatic vinyl group of C2-C60, aromatic amine group of C2-C60, condensed ring group of C2-C60 containing nitrogen atom, condensed ring group of C6-C60 containing phosphorus or silicon or boron atom and heterocyclic group of C2-C60 containing nitrogen atom;
d. a substituent-containing group c;
in the group b and the group d, the substituent is at least one selected from deuterium, C1-C20 aliphatic hydrocarbon group, halogen and cyano;
n is an integer of 1 to 5.
2. The compound of claim 1, wherein: in the formula I, R1And R2Are all selected from any one of the following groups:
in the above groups, A, B and C are each independently a carbon atom or a nitrogen atom, but A, B and C cannot be both nitrogen atoms,represents the position of a substituent;
R3any one selected from hydrogen, an aromatic group of C2-C60, an aromatic vinyl group of C2-C60, a condensed ring aromatic group of C2-C60, a condensed ring aromatic vinyl group of C2-C60, an aromatic amine group of C2-C60, a condensed ring group of C2-C60 containing a nitrogen atom, and a heterocyclic group of C2-C60 containing a nitrogen atom;
R4and R5Any one of aliphatic hydrocarbon groups of C1-C18, aromatic groups of C2-C60, condensed ring aromatic groups of C2-C60, aromatic amine groups of C2-C60, aromatic groups of C2-C60 connected with heterocycle and aromatic groups of C2-C60 connected with alkyl groups of C1-C18;
R6any one of aliphatic hydrocarbon groups of C1-C18, aromatic groups of C2-C60 and condensed ring aromatic groups of C2-C60;
R7any one selected from hydrogen, aliphatic hydrocarbon groups of C1-C18, aromatic groups of C2-C60, aromatic vinyl groups of C2-C60, fused ring aromatic groups of C2-C60 and fused ring aromatic vinyl groups of C2-C60;
d and E independently represent any one of an aromatic group of C2-C60, an aromatic vinyl group of C2-C60, a condensed ring aromatic group of C2-C60, a condensed ring aromatic vinyl group of C2-C60, a condensed ring group of C2-C60 and a heterocyclic group of C2-C60 containing a nitrogen atom;
f and G each independently represent a carbon atom or a nitrogen atom.
3. The compound of any one of claims 1-2, wherein: the compound shown in the formula I is any one of the following compounds:
4. a process for the preparation of a compound of formula I as claimed in any one of claims 1 to 3, comprising the steps of:
1) will be provided withUniformly mixing the catalyst, the ligand and the alkali in a solvent for ring closing reaction to obtain the catalyst
2) Subjecting the product obtained in step 1)Mixing with potassium scrap in solvent, coupling reacting, quenching reaction with mixed solution of tetrahydrofuran and water to obtain final product
3) Subjecting the product obtained in step 2)Uniformly mixing the compound with a catalyst, a phosphorus ligand and alkali, and refluxing to react to obtain a compound shown in the formula I;
in the steps 1) to 3), R in the structural general formula of each reactant1、R2And n is as defined in claim 1.
5. The method of claim 4, wherein: in the step 1), the catalyst is palladium acetate or Pd (PPh)3)4、Pd(PPh3)2Cl2Or Pd (dba)2；
The ligand is tri-tert-butylphosphine, triphenylphosphine or tricyclohexylphosphine;
the alkali is potassium carbonate, sodium carbonate, potassium acetate or sodium acetate;
the above-mentionedThe feeding molar usage of the catalyst, the ligand and the alkali is 1.0: 1.0-1.5: 0.01-0.05: 0.02-0.10: 2.0-3.0, specifically 1.0: 1.2: 0.02: 0.05: 2.5;
in the ring-closing reaction, the temperature is 100-150 ℃, and the time is 8-16 hours;
in the step 2) of the said step,the feeding molar amount of the potassium chips is 1.0: 1.0-5.0, specifically 1.0: 4.0;
in the mixed liquid composed of tetrahydrofuran and water, the volume ratio of tetrahydrofuran to water is 1.0: 1.0;
in the step of coupling reaction, the temperature is room temperature, and the time is 12-48 hours;
in the step 3), the catalyst is tris (dibenzylideneacetone) dipalladium, palladium acetate and Pd (PPh)3)4Or Pd (PPh)3)2Cl2Or Pd (dba)2；
The phosphorus ligand is 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, tri-tert-butylphosphine, triphenylphosphine or tricyclohexylphosphine;
the alkali is sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide or potassium hydroxide;
the feeding molar ratio of the catalyst to the phosphorus ligand to the alkali is 2.0-2.5: 1.0: 0.005-0.02: 0.01-0.05: 2.0-3.0, specifically 2.25: 1.0: 0.01: 0.04: 2.5;
in the reaction step, the time is 24-56 hours;
the steps 1) to 3) are all carried out in an inert atmosphere; the inert atmosphere is specifically nitrogen or argon atmosphere;
in the steps 1) to 3), the solvent is at least one selected from N-methylpyrrolidone, tetrahydrofuran, toluene, N-dimethylformamide and xylene.
6. A luminescent material comprising a compound of formula I according to any one of claims 1 to 3; or,
use of a compound of formula I according to any one of claims 1 to 3 for the preparation of a luminescent material;
the fluorescence emission wavelength of the luminescent material is specifically 370-420 nm.
7. An electroluminescent device comprising a compound of formula I as claimed in any one of claims 1 to 3;
use of a compound of formula I as claimed in any one of claims 1 to 3 for the preparation of an electroluminescent device.
8. The device or use according to claim 7, wherein: in the electroluminescent device, the compound shown in the formula I is a material for forming an organic light-emitting layer;
the electroluminescent device consists of a transparent substrate, an anode, a hole transport layer, an organic light emitting layer, an electron transport layer and a cathode layer from bottom to top in sequence;
wherein, the material for forming the transparent substrate is glass or a flexible substrate;
the anode layer is made of inorganic materials or organic conducting polymers; wherein the inorganic material is indium tin oxide, zinc oxide, tin oxide, gold, silver or copper; the organic conducting polymer is selected from at least one of polythiophene, sodium polyvinyl benzene sulfonate and polyaniline;
the material constituting the hole transport layer is selected from at least one of TDATA and NPB;
the structural formula of the NPB is as follows:
the structural formula of the TDATA is as follows:
the organic light-emitting layer is composed of a compound represented by formula I of claim 1 anda mixture of components; the compounds of the formula I andthe mass ratio of (1): 0.001-0.2, specifically 1: 0.08;
the material for forming the electron transport layer is Alq3, Gaq3 or BPhen;
wherein the structural formulas of Alq3, BPhen and Gaq3 are as follows in sequence:
the cathode layer is made of a material selected from any one or two of the following elements: lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold, and silver.
9. Use according to claim 8 or an organic electroluminescent device according to claim 7, characterized in that:
the thickness of the hole transport layer is 5-15nm, specifically 10 nm;
the thickness of the organic light-emitting layer is 10-100nm, specifically 80 nm;
the thickness of the electron transmission layer is 40-60nm, specifically 50 nm;
the thickness of the cathode layer is 90-110nm, specifically 100 nm.
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Application publication date: 20140723