CN110698458A - Organic luminescent material and application thereof - Google Patents

Organic luminescent material and application thereof Download PDF

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CN110698458A
CN110698458A CN201911044521.6A CN201911044521A CN110698458A CN 110698458 A CN110698458 A CN 110698458A CN 201911044521 A CN201911044521 A CN 201911044521A CN 110698458 A CN110698458 A CN 110698458A
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邢其锋
丰佩川
陈跃
胡灵峰
陈义丽
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YANTAI XIANHUA CHEM-TECH Co Ltd
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YANTAI XIANHUA CHEM-TECH Co Ltd
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Abstract

The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an organic luminescent material and application thereof. The organic luminescent material has a parent structure of indolocarbazole, high bond energy among atoms, good thermal stability and favorability for intermolecular solid-state accumulation. The preparation process of the derivative is simple and easy to implement, the raw materials are easy to obtain, and the derivative is suitable for mass production and amplification. The arylamine substituted indole heterocyclic ring derivative is applied to a light-emitting layer of an organic electroluminescent device, has a proper energy level with an adjacent layer, is favorable for injecting holes and electrons, can effectively reduce the starting voltage, has a high exciton migration rate, and can realize good light-emitting efficiency in the device. The compound has a larger conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability, and has long service life as a luminescent layer material in an organic electroluminescent device.

Description

Organic luminescent material and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an organic luminescent material and application thereof.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by a current and an electric field under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, a film can be formed on any substrate by an evaporation or spin coating method, and flexible display and large-area display can be realized; the optical property, the electrical property, the stability and the like of the material can be adjusted by changing the structure of molecules, and the selection of the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. The phosphorescent host materials used at present often have single carrier transport capability, such as hole-based transport hosts and electron-based transport hosts, but the single carrier transport capability may cause mismatching of electrons and holes in the light emitting layer, thereby causing severe efficiency roll-off and shortened lifetime.
CN102558121A reports a fused heterocyclic structure substituted by arylamine as a main material, the material belongs to a cavity type material, and the luminous efficiency and the service life of the material are improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an organic luminescent material and application thereof.
The technical scheme for solving the technical problems is as follows: an organic light-emitting material, the structural formula of which is as follows:
Figure BDA0002253773850000021
wherein Ar is1、Ar2Each independently is substituted or unsubstituted C6-C30Any one of the aromatic group or the heteroaromatic group of (a);
Ar3is substituted or unsubstituted N-containing C5-C30Any of the heteroaryl groups of (a);
R1-R6each independently is hydrogen, C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Any one of heteroaryl;
x, Y are each independently a bond, O, S, CR7R8Or NR9And at least one is not a chemical bond;
wherein R is7、R8Each independently is C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Any one of heteroaryl; r9Is substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Any one of heteroaryl groups.
Further, Ar1、Ar2Each independently is any one of a substituted or unsubstituted phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrenyl group, triphenylene group, fluorenyl group, benzofuranyl group, dibenzofuranyl group, aza-dibenzofuranyl group, benzothienyl group, dibenzothienyl group, aza-dibenzothienyl group, phenanthrenyl group, 9-dimethylfluorenyl group, spirofluorenyl group, arylamine group, or carbazolyl group.
Ar3Is a substituted or unsubstituted pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, or pyridopyrazinyl group.
Further, R1-R6Each independently is any one of hydrogen, deuterium, methyl, ethyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
Further, Ar is1-Ar3、R1-R9Wherein the substituents of the selected groups are each independently hydrogen, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl ofAny one of the above.
Further, R1-R6Any two adjacent groups are connected by chemical bonds to form a ring.
Further, the structural formula of the organic light emitting material is preferably as follows:
Figure BDA0002253773850000041
Figure BDA0002253773850000051
Figure BDA0002253773850000061
Figure BDA0002253773850000071
the second purpose of the invention is to provide the application of the organic luminescent material in an organic electroluminescent device.
An organic electroluminescent device comprises a substrate, an anode layer, an organic layer at least comprising a light-emitting layer, and a cathode layer sequentially formed on the substrate;
wherein the host material of the light-emitting layer comprises at least one organic light-emitting material of the present invention.
Further, the organic layer may further include one or more of a hole injection layer, a hole blocking layer, an electron transport layer, or an electron injection layer.
The invention has the beneficial effects that:
1. the organic luminescent material has a parent structure of indolocarbazole, high bond energy among atoms, good thermal stability and favorability for intermolecular solid-state accumulation. The preparation process of the derivative is simple and easy to implement, the raw materials are easy to obtain, and the derivative is suitable for mass production and amplification.
2. The arylamine substituted indole heterocyclic ring derivative is applied to a light-emitting layer of an organic electroluminescent device, has a proper energy level with an adjacent layer, is favorable for injecting holes and electrons, can effectively reduce the starting voltage, has a high exciton migration rate, and can realize good light-emitting efficiency in the device. The compound has a larger conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability, and has long service life as a luminescent layer material in an organic electroluminescent device.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Synthesis of Compound A1, the reaction equation is as follows:
Figure BDA0002253773850000081
the synthesis method comprises the following steps:
(1) 21.2g (100mmol) of 4-dibenzofuranboronic acid, 32.6g (100mmol) of 2-iodo-5-bromonitrobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction solution by ethyl acetate, and concentrating an organic phase to obtain a yellow solid A;
(2) adding 100mmol of the intermediate A into 1000mL of o-dichlorobenzene solution, adding (300mmol) of triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate B;
(3) in a reaction flask, add (100mmol) of intermediate B, 16.5g (100mmol) of diphenylamine, 0.9g (0.785mmol, 0.5%) of Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate C;
(4) adding (100mmol) intermediate C, 2-chloro-4-phenylquinazoline (100mmol), potassium carbonate 40g (300mmol) and 1000mL DMF in a reaction bottle, and reacting at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 1.
1H NMR(400MHz,Chloroform)δ8.59(s,1H),8.01(dd,J＝8.4,6.4Hz,4H),7.94–7.92(m,1H),7.79(t,J＝2.2Hz,4H),7.65(s,2H),7.59(s,2H),7.56–7.48(m,3H),7.39(s,1H),7.31(s,1H),7.24(s,4H),7.08(s,5H),7.00(s,2H),6.40(s,1H)。
Example 2
Synthesis of Compound A5, the reaction equation is as follows:
Figure BDA0002253773850000091
the synthesis method comprises the following steps:
(1) 21.2g (100mmol) of 4-dibenzofuranboronic acid, 32.6g (100mmol) of 2-iodo-5-bromonitrobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction solution by ethyl acetate, and concentrating an organic phase to obtain a yellow solid A;
(2) adding 100mmol of the intermediate A into 1000mL of o-dichlorobenzene solution, adding (300mmol) of triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate B;
(3) a reaction flask was charged with (100mmol) of intermediate B, 16.5g (100mmol) of 2- (9, 9-dimethylfluorene) -aniline, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate C;
(4) adding (100mmol) of the intermediate C, 2-chloro-4- (3-dibenzothienyl) quinazoline (100mmol), 40g of potassium carbonate (300mmol) and 1000mL of DMF (dimethyl formamide) into a reaction bottle, and reacting at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 5.
1H NMR(CDCl3,400MHz)δ8.59(s,1H),8.43(d,J＝4.0Hz,2H),8.10(s,1H),8.03(s,1H),7.94(t,J＝6.0Hz,3H),7.90–7.81(m,4H),7.77(s,1H),7.66(d,J＝7.2Hz,3H),7.65–7.50(m,6H),7.40–7.27(m,5H),7.22(d,J＝8.0Hz,3H),7.06(s,2H),6.98(s,1H),6.38(s,1H),1.68(s,12H)。
Example 3
Synthesis of Compound A13, the reaction equation is as follows:
Figure BDA0002253773850000101
the synthesis method comprises the following steps:
(1) 21.2g (100mmol) of 1-dibenzothiophene boronic acid, 32.6g (100mmol) of 2-iodo-5-bromonitrobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction solution by ethyl acetate, and concentrating an organic phase to obtain a yellow solid A;
(2) adding 100mmol of the intermediate A into 1000mL of o-dichlorobenzene solution, adding (300mmol) of triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate B;
(3) to a reaction flask, add (100mmol) intermediate B, (100mmol)2- (2-naphthyl) -aniline, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate C;
(4) adding (100mmol) intermediate C, 2-chloro-4-phenylquinazoline (100mmol), potassium carbonate 40g (300mmol) and 1000mL DMF in a reaction bottle, and reacting at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 13.
1H NMR(CDCl3,400MHz)δ8.73(s,2H),8.45(s,2H),8.13(s,1H),7.97(d,J＝12.4Hz,6H),7.85(d,J＝8.0Hz,8H),7.80(d,J＝9.6Hz,6H),7.71(s,4H),7.63(d,J＝16.0Hz,7H),7.58–7.50(m,7H),7.50–7.40(m,6H),7.38(s,2H),7.31(s,2H),7.24(s,4H),7.10(d,J＝12.0Hz,6H),7.00(s,2H),6.40(s,2H)。
Example 4
Synthesis of Compound A25, the reaction equation is as follows:
Figure BDA0002253773850000121
the synthesis method comprises the following steps:
(1) 21.2g (100mmol) of 4-dibenzofuranboronic acid, 32.6g (100mmol) of 2-iodo-5-bromonitrobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction solution by ethyl acetate, and concentrating an organic phase to obtain a yellow solid A;
(2) adding 100mmol of the intermediate A into 1000mL of o-dichlorobenzene solution, adding (300mmol) of triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate B;
(3) in a reaction flask, add (100mmol) intermediate B, (100mmol) diphenylamine, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate C;
(4) adding (100mmol) intermediate C, 2-chloro-3- (3-biphenyl) quinoxaline (100mmol), potassium carbonate 40g (300mmol) and 1000mL DMF in a reaction bottle, and reacting at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 25.
1H NMR(CDCl3,400MHz)δ8.47(d,J＝14.0Hz,2H),8.03–7.91(m,6H),7.78(s,3H),7.75(d,J＝6.0Hz,1H),7.63(m,6H),7.38(d,J＝10.0Hz,2H),7.29(s,1H),7.22(s,4H),7.07(s,2H),6.99(s,3H),6.39(s,2H)。
Example 5
Synthesis of Compound A27, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) taking (100mmol) N-phenylcarbazole-1-boric acid, 32.6g (100mmol) 2-iodine-5-bromonitrobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction solution by ethyl acetate, and concentrating an organic phase to obtain a yellow solid A;
(2) adding 100mmol of the intermediate A into 1000mL of o-dichlorobenzene solution, adding (300mmol) of triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate B;
(3) to a reaction flask, add (100mmol) of intermediate B, (100mmol) (4-biphenyl) -aniline, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate C;
(4) adding (100mmol) intermediate C, 2-chloro-4-phenylquinazoline (100mmol), potassium carbonate 40g (300mmol) and 1000mL DMF in a reaction bottle, and reacting at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 27.
1H NMR(CDCl3,400MHz)δ8.55(s,1H),8.15(s,1H),8.15–7.95(m,2H),7.95–7.82(m,1H),7.95–7.76(m,5H),7.75(s,1H),7.76–7.47(m,11H),7.39(d,J＝10.0Hz,3H),7.28–7.24(m,1H),7.24(s,2H),7.16(s,1H),7.10(d,J＝12.0Hz,3H),7.00(s,2H),6.40(s,1H)。
Example 6
Synthesis of Compound A37, the reaction equation is as follows:
the synthesis method comprises the following steps:
(1) taking (100mmol)4- (9, 9-dimethylfluorene) boric acid, 32.6g (100mmol) 2-iodine-5-bromonitrobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction solution by ethyl acetate, and concentrating an organic phase to obtain a yellow solid A;
(2) adding 100mmol of the intermediate A into 1000mL of o-dichlorobenzene solution, adding (300mmol) of triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate B;
(3) in a reaction flask, add (100mmol) intermediate B, (100mmol) diphenylamine, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate C;
(4) adding (100mmol) intermediate C, 2-chloro-3- (3-biphenyl) quinoxaline (100mmol), potassium carbonate 40g (300mmol) and 1000mL DMF in a reaction bottle, and reacting at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 37.
1H NMR(CDCl3,400MHz)δ8.54(d,J＝6.8Hz,1H),8.24(s,1H),7.96(s,1H),7.83(d,J＝7.6Hz,2H),7.75(m,6H),7.65(t,J＝10.0Hz,4H),7.53(s,1H),7.49(s,2H),7.41(s,1H),7.34(s,1H),7.24(m,4H),7.21(s,1H),7.14(d,J＝10.0Hz,4H),7.00(s,1H),6.40(s,1H),1.69(m,6H)。
Example 7
Synthesis of Compound A46, the reaction equation is as follows:
Figure BDA0002253773850000151
the synthesis method comprises the following steps:
(1) taking (100mmol) 4-bromophenoxazine, (100mmol) iodobenzene, and 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate M1;
(2) into a reaction flask, M1 (100mmol), (120mmol) pinacol diboron, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and potassium acetate (300mmol) at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate M2;
(3) into a reaction flask, M2 (100mmol), 32.6g (100mmol) of 2-iodo-5-bromonitrobenzene, and Pd (1%) in (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M3;
(4) adding (100mmol) intermediate M3, 1000mL o-dichlorobenzene solution and (300mmol) triphenylphosphine into a reaction bottle, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M4;
(5) in a reaction flask, add (100mmol) intermediate M4, (100mmol) diphenylamine, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate M5;
(6) adding (100mmol) intermediate M5, 2-chloro-3- (3-biphenyl) quinoxaline (100mmol), potassium carbonate 40g (300mmol) and 1000mL DMF in a reaction flask, and reacting at 120 ℃ for 12 h; after the reaction was complete, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give a yellow powder a 46.
1H NMR(CDCl3,400MHz)δ8.28–7.95(m,4H),7.95(s,1H),7.88–7.76(m,5H),7.65-7.56(m,6H),7.45(t,J＝11.2Hz,3H),7.24-7.14(m,3H),7.08–6.96(m,9H),6.40(s,1H)。
Example 8
Synthesis of Compound A67, the reaction equation is as follows:
Figure BDA0002253773850000171
the synthesis method comprises the following steps:
(1) 21.2g (100mmol) of 4-dibenzofuranboronic acid, 32.6g (100mmol) of 2-iodo-5-bromonitrobenzene, (1%) Pd (PPh3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M1;
(2) adding (100mmol) M1 and 1000mL o-dichlorobenzene solution into a reaction bottle to neutralize (300mmol) triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M2;
(3) into a reaction flask, M2 (100mmol), 16.5g (100mmol) of 2- (9, 9-dimethylfluorene) Aniline, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate M3;
(4) to a reaction flask was added (100mmol) intermediate M3, 2- (4-bromobenzene) -4, 6-diphenyl-triazine (100mmol), 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; after the reaction was completed, the reaction was stopped, and the reaction product was cooled to room temperature, extracted with water and ethyl acetate, concentrated, and subjected to column chromatography with an organic phase, and the obtained solid was purified by recrystallization from toluene to obtain yellow powder a 67.
1H NMR(CDCl3,400MHz)δ8.36-8.29(m,3H),7.97(d,J＝10.0Hz,4H),7.91(d,J＝8.0Hz,4H),7.71(d,J＝11.2Hz,4H),7.60(s,1H),7.52–7.40(m,7H),7.39-7.24(m,9H),7.08-7.00(m,5H)。
Example 9
Synthesis of Compound A77, the reaction equation is as follows:
Figure BDA0002253773850000181
the synthesis method comprises the following steps:
(1) into a reaction flask were added (100mmol) 1-bromo-2-hydroxynaphthalene, pinacol diboron (120mmol), 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate M1;
(2) taking (100mmol) M1, (100mmol) 2-bromo-3-chlorofluorobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; reaction solutionExtracting with ethyl acetate, and concentrating the organic phase to obtain yellow solid M2;
(3) taking (100mmol) M2, (1%) Pd (OAc)2Heating 40g (300mmol) of sodium carbonate and 500mL of DMF (dimethyl formamide) to reflux, and reacting for 8 hours; extracting the reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M3;
(4) into a reaction flask, M3 (100mmol), pinacol diborate (120mmol), 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain an intermediate M4;
(5) taking (100mmol) M4, 32.6g (100mmol) 2-iodo-5-bromonitrobenzene and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M5;
(6) adding (100mmol) M5 and 1000mL o-dichlorobenzene solution into a reaction bottle to neutralize (300mmol) triphenylphosphine, heating to reflux, reacting for 12h, and finishing the reaction; evaporating to remove solvent, performing silica gel column chromatography, and separating to obtain intermediate M6;
(7) taking (100mmol) 2-chloro-3-phenylquinoxaline, (100mmol) 3-trifluoromethyl-4-fluorobenzeneboronic acid and (1%) Pd (PPh)3)4Heating 40g (300mmol) of sodium carbonate, toluene (800mL), ethanol (200mL) and water (200mL) to reflux, and reacting for 8 h; extracting the reaction liquid by ethyl acetate, and concentrating an organic phase to obtain a yellow solid M7;
(8) adding the intermediate M6 (100mmol) and M7 (100mmol) into a reaction bottle, continuously adding potassium carbonate (300mmol) and DMF (500mL), heating to 120 ℃, reacting for 8h, cooling after the reaction is finished, adding water into the reaction liquid, separating out a solid, filtering, and drying to obtain an intermediate M8;
(9) into a reaction flask, M8 (100mmol), (100mmol) 2-triphenylene-aniline, 0.9g (0.785mmol, 0.5%) Pd2(dba)31500mL of toluene and 40g (300mmol) of sodium tert-butoxide, and reacting at 100 ℃ for 5 h; stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water and ethyl acetate for extraction, concentrating, carrying out organic phase column chromatography, and recrystallizing and purifying the obtained solid in toluene to obtain the final product A77.
1H NMR(CDCl3,400MHz)δ8.54(s,1H),8.33(t,J＝12.0Hz,4H),8.31(t,J＝7.2Hz,2H),8.30-8.15(m,3H),8.00–7.87(m,8H),7.80(s,1H),7.72–7.54(m,7H),7.54–7.48(m,5H),7.31(d,J＝12.0Hz,3H),7.24(s,1H),6.46(d,J＝11.2Hz,4H).
The other compounds of the present invention can be synthesized by selecting raw materials with suitable structures according to the above-mentioned ideas of examples 1-9, and the synthesis process is not repeated here.
Device application example
The organic light emitting diode selected in the device application example of the present invention includes a first electrode and a second electrode on a substrate, and an organic layer between the electrodes, and the organic layer may be a multilayer structure. For example, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. The substrate is a conventional substrate used in an organic light emitting display in the related art, for example, glass, polymer materials, glass and polymer materials with TFT components, and the like.
The anode material may be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) known in the art2) Transparent conductive materials such as zinc oxide (ZnO), metal materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT, and a combination of the above materials in a multilayer structure.
The cathode material can be selected from materials and structural combinations of metals such as magnesium silver mixture, LiF/Al, ITO and the like, metal mixtures, oxides and the like.
The OLED device may also include a hole injection layer, a hole transport layer, between the light emitting layer and the anode, which may be, but is not limited to, a combination of one or more of HT1-HT31 listed below.
Figure BDA0002253773850000211
Figure BDA0002253773850000221
The device light emitting layer may comprise a host material and a light emitting dye, wherein the host material includes, but is not limited to, one or more combinations of conventional materials as shown in GPH1-GPH80 below.
Figure BDA0002253773850000222
Figure BDA0002253773850000231
Figure BDA0002253773850000241
In one aspect of the invention, the emissive layer employs a phosphorescent electroluminescent technology, and the emissive layer phosphorescent dopant (luminescent dye) may be selected from, but is not limited to, a combination of one or more of RPD-1 through RPD-28 listed below.
Figure BDA0002253773850000251
The electron transport layer materials include, but are not limited to, one or a combination of more of the ET1-ET57 materials listed below.
Figure BDA0002253773850000252
Figure BDA0002253773850000271
Figure BDA0002253773850000281
The device may further comprise an electron injection layer between the electron transport layer and the cathode, and the electron injection layer comprises, but is not limited to, LiQ, LiF, NaCl, CsF, Li in the prior art2O、Cs2CO3One or a combination of more of materials such as BaO, Na, Li, Ca and the like.
The preparation process of the organic electroluminescent device in the application example of the device is as follows:
the following compounds were used as controls:
Figure BDA0002253773850000282
(1) ultrasonically treating the glass plate coated with the ITO transparent conducting layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent, baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 10 DEG-5Pa, vacuum evaporating HT-11 on the anode layer film to form a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
(3) evaporating HT-5 material on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
(4) a light-emitting layer of the device is evaporated in vacuum on the hole transport layer, wherein the light-emitting layer comprises a main material and a dye material, the main material is evaporated by respectively selecting the compound and the material R1 in the embodiments 1-9 by a multi-source co-evaporation method, the evaporation rate of the main material is adjusted to be 0.1nm/s, the evaporation rate is set according to the proportion of 3% of the evaporation of the dye RPD-1, and the total thickness of the evaporation film is 30 nm;
(5) an electron transport layer of the device is evaporated on the light-emitting layer in vacuum, and an ET42 material is selected, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
(6) LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the organic electroluminescent device obtained in the application example and the comparative example was measured for driving voltage, current efficiency and lifetime at the same luminance using a digital source meter and a luminance meter, specifically, for increasing the voltage at a rate of 0.1V per second, and it was measured that the luminance of the organic electroluminescent device reached 5000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 5000cd/m2The luminance drop of the organic electroluminescent device was measured to be 4750cd/m by maintaining a constant current at luminance2Time in hours.
The properties of the organic electroluminescent devices prepared from the host material of the present invention and the host material R1 of the prior art are shown in Table 1 below.
TABLE 1
Figure BDA0002253773850000291
As can be seen from the data in Table 1, the novel organic material prepared by the invention is used as a main material of an organic electroluminescent device, can effectively reduce the rise-fall voltage, improve the current efficiency and prolong the service life of the device, and is a main material with good performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. An organic light-emitting material, characterized in that it has the following structural formula:
Figure FDA0002253773840000011
wherein Ar is1、Ar2Each independently is substituted or unsubstituted C6-C30Any one of the aromatic group or the heteroaromatic group of (a);
Ar3is substituted or unsubstituted N-containing C5-C30Any of the heteroaryl groups of (a);
R1-R6each independently is hydrogen, C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Any one of heteroaryl;
x, Y are each independently a bond, O, S, CR7R8Or NR9And at least one is not a chemical bond;
wherein R is7、R8Each independently is C1-C10Alkyl radical, C1-C6Cycloalkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Any one of heteroaryl; r9Is substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Any one of heteroaryl groups.
2. The organic light-emitting material according to claim 1, wherein Ar is Ar1、Ar2Each independently a substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranylAny one of furyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
3. The organic light-emitting material according to claim 1, wherein Ar is Ar3Is a substituted or unsubstituted pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, or pyridopyrazinyl group.
4. The organic light-emitting material according to claim 1, wherein R is1-R6Each independently is any one of hydrogen, deuterium, methyl, ethyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, phenanthryl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, or carbazolyl.
5. The organic light-emitting material according to any one of claims 1 to 4, wherein Ar is Ar1-Ar3、R1-R9Wherein the substituents of the selected groups are each independently hydrogen, halogen, nitro, cyano, C1-C4Any one of alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
6. The organic light-emitting material according to claim 1, wherein R is1-R6Any two adjacent groups are connected by chemical bonds to form a ring.
7. The organic light-emitting material according to claim 1, having a structural formula of:
Figure FDA0002253773840000031
Figure FDA0002253773840000051
8. use of the organic light-emitting material according to any one of claims 1 to 7 in an organic electroluminescent device.
9. An organic electroluminescent element comprising a first electrode, a second electrode and an organic layer comprising at least one light-emitting layer interposed between the first electrode and the second electrode, wherein the organic layer contains the compound according to any one of claims 1 to 7.
CN201911044521.6A 2019-10-30 2019-10-30 Organic luminescent material and application thereof Pending CN110698458A (en)

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