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CN110372570B - Amine derivative of fluorenocarbazole and preparation method and application thereof - Google Patents

Amine derivative of fluorenocarbazole and preparation method and application thereof Download PDF

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CN110372570B
CN110372570B CN201810327166.2A CN201810327166A CN110372570B CN 110372570 B CN110372570 B CN 110372570B CN 201810327166 A CN201810327166 A CN 201810327166A CN 110372570 B CN110372570 B CN 110372570B
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fluorenocarbazole
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hole transport
amine derivative
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穆广园
庄少卿
任春婷
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Wuhan Shangsai Optoelectronics Technology Co ltd
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Abstract

The invention relates to an amine derivative of fluorenocarbazole and a preparation method and application thereof. The amine derivative of fluorenocarbazole provided by the invention modifies the fluorenocarbazole with condensed ring rigid and dense structure by introducing the functional group rich in the hole site, so that a non-crystalline compound with asymmetric and large steric hindrance is formed, and the non-crystalline compound has good thermal stability and film forming property, and has remarkable progress in the aspects of starting voltage, luminous brightness, current efficiency, lumen efficiency, external quantum efficiency and the like when being applied to an organic electroluminescent device as a hole transport material, an electronic barrier material and/or a light emitting layer material, compared with an organic electroluminescent device prepared by a traditional hole transport material, and the amine derivative of fluorenocarbazole is an ideal hole transport material, an electronic barrier material and a light emitting layer material.

Description

Amine derivative of fluorenocarbazole and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoelectric material application, and particularly relates to an amine derivative of fluorenocarbazole, and a preparation method and application thereof.
Background
An Organic Light-emitting Diode (OLED), also known as an Organic electroluminescent device or an Organic Light-emitting Display (OLED), is a solid semiconductor Light-emitting technology using Organic materials. The device mainly adopts organic micromolecule/high polymer semiconductor materials, and the organic micromolecule and the high polymer materials have the characteristics of easy preparation, processing and purification and high-selectivity modification, so that the device has great potential in the field of material application, and the device becomes a focus in both research and commerce. Compared with relatively mature inorganic semiconductor materials, organic/polymer semiconductor materials can be applied to semiconductor devices such as electroluminescent diodes, field effect transistors, organic lasers, photovoltaic cells, sensors and the like. As the most important 25 inventions in 25 years, the organic light emitting diode has undergone a rapid development process, and has attracted attention from new material development, device structure preparation, mechanism exploration and market promotion, and has become a representative and innovative flag in the semiconductor field.
An organic light emitting diode generally consists of an electrode, an electron/hole injection layer, an electron/hole transport layer, and a light emitting layer, and correspondingly includes a cathode/anode electrode, an electron/hole injection material, an electron/hole transport material, and a light emitting material. The high efficiency organic electroluminescent device requires a low operating voltage, high current efficiency, and relatively good stability. However, in organic semiconductor materials, the mobility of holes is usually much higher than that of electrons, which leads to the imbalance of electron and hole injection in the light emitting layer of the OLED device, and the difference between the mobilities of electrons and holes is large, which easily causes quenching of excitons in the light emitting region near the electron transport layer with small mobility and the cathode side, thus reducing the efficiency and brightness of the OLED device and affecting the overall performance of the device. Therefore, the development of materials and the adjustment of device structures for improving the efficiency of hole recombination in the light-emitting layer have been the hot spots of research in the field of optoelectronic technology.
Disclosure of Invention
In order to overcome the defects in the prior art, the first aspect of the invention provides a fluorenocarbazole amine derivative, which has the following structural formula:
Figure BDA0001626958080000021
wherein R is1、R2、R3Is substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C11-C30Any one of the heteroaryl groups of (a);
the R is1、R2And R3The same or different.
Preferably, said R is1And R2Is substituted or unsubstituted C6-C24Non-condensed ring aromatic group of (A), substituted or unsubstituted C10-C30A condensed ring aromatic group of (C), substituted or unsubstituted11-C30Any one of the fused heterocyclic groups of (1).
Preferably, said R is1And R2Is substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, dibenzofuranyl which is unsubstituted or substituted by alkyl, dibenzothiophenyl which is unsubstituted or substituted by alkyl, carbazolyl which is unsubstituted or substituted by alkyl, fluorenyl which is unsubstituted or substituted by alkyl or aryl, spirobifluorenyl which is unsubstituted or substituted by alkyl or aryl.
Wherein, dibenzofuranyl which is unsubstituted or substituted by alkyl, dibenzothienyl which is unsubstituted or substituted by alkyl, carbazolyl which is unsubstituted or substituted by alkyl are all condensed heterocyclic groups; the fluorenyl group which is unsubstituted or substituted by an alkyl group or an aromatic group, and the spirobifluorenyl group which is unsubstituted or substituted by an alkyl group or an aromatic group are all fused ring aromatic groups.
As a preferable technical means of the present invention, R is1And R2Is any one of the following unsubstituted or substituted by alkyl:
Figure BDA0001626958080000031
wherein, is a site linked to N of the amine group, R1And R2The same or different. Preferably, the first and second liquid crystal materials are,
the structures of R1 and R2 are as follows:
Figure BDA0001626958080000041
wherein x is the site attached to N on the amine group.
As a preferable technical means of the present invention, R is3Is any one of the following unsubstituted or substituted by alkyl:
Figure BDA0001626958080000042
wherein x is a site to which N of carbazole is bonded.
The following are examples of the structures described by the general formula of the present invention, but the structures included in the claims are not limited to the examples.
Figure BDA0001626958080000051
Figure BDA0001626958080000061
Figure BDA0001626958080000071
Figure BDA0001626958080000081
Figure BDA0001626958080000091
Figure BDA0001626958080000101
Figure BDA0001626958080000111
Figure BDA0001626958080000121
Figure BDA0001626958080000131
The second aspect of the present invention provides a method for preparing an amine derivative of fluorenocarbazole, comprising the steps of:
Figure BDA0001626958080000141
wherein R is1、R2、R3Is substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C11-C30Any one of the heteroaryl groups of (a);
the R is1、R2And R3The same or different.
In the above reaction step, R is1-NH2The substitution reaction with Br-containing compound belongs to the reaction of amine and halohydrocarbon, which is a typical Ullmann reaction, and because H on NH is more active, the Br substitution position in the Br-containing compound is R1-NH2At N-H in (1). Similarly, in the above reaction step, R2The substitution reaction between-Br and d compound belongs to the reaction of amine and halohydrocarbon, which is a typical Ullmann reaction, and because H on NH is more active, the Br substitution position in the Br-containing compound is N-H in the d compound; r3The substitution reaction between-Br and f compound is amine reaction with halohydrocarbon, which is typical Ullmann reaction, because H on NH is more active, the Br substitution position in Br-containing compound is N-H in f compound.
In detail, the preparation process of the amine derivative of fluorenocarbazole is as follows:
(1) reacting the reactant 2-bromo-7-iodo-9, 9-dimethyl-9H-fluorene, 2-chloroaniline and palladium acetate (Pd (OAc)2) Tri-tert-butylphosphine (P (t-Bu)3)、Sodium tert-butoxide (NaOBu)t) Feeding materials according to the molar ratio of 1:1: 3: 6: 2, adding Toluene (Toluene) with the volume of 5-15 times, heating to 100-120 ℃ in a nitrogen atmosphere, reacting for 5-20 h, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, washing with water, filtering, recrystallizing with ethanol for two to three times, and drying to obtain an intermediate a;
(2) the intermediate a, palladium acetate, Diazabicyclo (DBU), tri-tert-butylphosphine (P (t-Bu)3) Feeding materials according to a molar ratio of 1:0.1:0.1:2.5, adding 2-10 times of volume of O-xylene (O-xylene) and 2-10 times of volume of N, N-Dimethylaniline (DMA), heating to 150 ℃ in a nitrogen atmosphere to react for 5-20 h, completing liquid phase monitoring reaction, washing for 2-3 times, filtering, pulping with ethanol for two to three times, and drying to obtain an intermediate b;
(3) feeding the intermediate b and sodium hydride (NaH) according to a molar ratio of 1:1.1, adding Tetrahydrofuran (THF) with the volume of 5-15 times, stirring for 5-10 minutes at 0 ℃ under the atmosphere of nitrogen, slowly adding 1.2 times (calculated according to the amount of the intermediate b) of p-toluenesulfonic acid by using a dropping funnel, naturally heating the reaction liquid to room temperature, slowly adding water to quench the reaction after overnight, adding ethyl acetate to extract, separating, concentrating and drying to obtain an intermediate c;
(4) intermediate c and R1Corresponding substituted amide, tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Tri-tert-butylphosphine (P (t-Bu)3) Sodium tert-butoxide (NaOBu)t) Charging according to the molar ratio of 1:1: 3: 6: 2, adding 3-15 times of Toluene (Toluene) in volume, heating to 100-120 ℃ in nitrogen atmosphere for reaction for 5-20 h, monitoring the completion of the reaction by liquid phase, cooling, adding 1 time of R (calculated according to the amount of the substance of the intermediate c)2Heating the corresponding substituted bromide to 100-120 ℃, continuing to react for 5-20 h, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain an intermediate e;
(5) feeding the intermediate e and sodium hydroxide (NaOH) according to a molar ratio of 1:2, adding 2-10 times of ethanol, heating to 60-85 ℃ in a nitrogen atmosphere, reacting for 2-4 h, monitoring the reaction completion of a liquid phase, cooling to room temperature, and concentrating to obtain an intermediate f;
(6) intermediate f, R3Corresponding substituted bromide, tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Tri-tert-butylphosphine (P (t-Bu)3) Sodium tert-butoxide (NaOBu)t) Feeding materials according to the molar ratio of 1:1: 3: 6: 2, adding Toluene (Toluene) with the volume of 5-15 times, heating to 100-120 ℃ in a nitrogen atmosphere, reacting for 5-20 h, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain a final product g.
The third aspect of the invention provides an application of the amine derivative of fluorenocarbazole, wherein the amine derivative of fluorenocarbazole is used for manufacturing organic electroluminescent devices, organic solar cells, organic thin film transistors, organic light-emitting transistors and/or organic field effect transistors.
The fourth aspect of the present invention provides an organic electroluminescent device, which is formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode and a light emitting layer, wherein the hole transport layer, the electron blocking layer, the light emitting layer and/or the light emitting layer contain the amine derivative of fluorenocarbazole provided by the present invention.
The compound provided by the invention modifies fluorene carbazole with condensed ring rigidity and dense structure by introducing functional groups rich in hole sites, particularly condensed ring or condensed heterocyclic functional groups with a highly conjugated system, so as to form a series of highly asymmetric non-crystalline compounds with larger steric hindrance, wherein the formation of an intramolecular twisted pi conjugated system and the synergistic effect of a cross-linked structure effectively reduce the cohesive force between molecules, so that the compound has good thermal stability and film forming property, and can be used as a hole transport material for preparing devices, thereby effectively improving the local aggregation problem of the amorphous hole transport material caused by more joule heat generated at the interface of an anode and the hole transport layer in the continuous working process of the devices, and the proper HOMO-LUMO energy level (highest occupied molecular orbital-lowest unoccupied molecular orbital) ensures that the energy barrier between the compound and an injection layer and a luminescent layer is smaller, is an ideal hole transport material. Meanwhile, the compound provided by the invention has good capability of blocking electrons, and can effectively solve the problem that excitons are not attenuated by radiation because electrons are gathered at the interface of a hole transport layer and a light emitting layer when being used as an electron blocking layer material to prepare an organic electroluminescent device, so that the compound is an ideal electron blocking layer material. In addition, when the organic electroluminescent device is prepared as a light-emitting layer, the intensive structure of the compound can effectively alleviate the surface plasma absorption in the cathode when the organic electroluminescent device emits light, so that the light extraction efficiency is obviously improved, and the compound is also an ideal light-emitting layer material.
Drawings
Fig. 1 is an energy level diagram of a device 5 prepared in device example 5;
fig. 2 is a graph of voltage-luminance characteristics of devices 5 and 12 prepared in device example 5 and device example 12;
fig. 3 is a graph of luminance-current efficiency characteristics of devices 5 and 12 prepared in device example 5 and device example 12;
fig. 4 is a graph of luminance versus external quantum efficiency characteristics of devices 5 and 12 prepared in device example 5 and device example 12.
Detailed Description
The present invention will be further described with reference to the following examples. Any simple modifications, equivalent changes and the like to the following embodiments according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention. The present invention is not limited to the contents described in the following embodiments.
Example 1
The compound (8) of the present invention can be synthesized by the following method.
Figure BDA0001626958080000171
(1) Adding reactants 2-bromo-7-iodo-9, 9-dimethyl-9H-fluorene (79.81g, 200mmol), 2-chloroaniline (25.51g, 200mmol), palladium acetate (1.35g, 6mmol), tri-tert-butylphosphine (2.43g, 12mmol), sodium tert-butoxide (38.44g, 400mmol) and 800ml of toluene into a 2L reaction flask, heating to 110 ℃ under nitrogen atmosphere, reacting for 8H, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, washing with water, filtering, recrystallizing with ethanol twice, and drying to obtain an intermediate a69.38g with a yield of 87%;
(2) adding the intermediate a (59.80g, 150mmol), palladium acetate (3.37g, 15mmol), diazabicyclo (2.28g, 15mmol), tri-tert-butylphosphine (75.87g, 375mmol), 400ml o-xylene and 200ml N, N-dimethylaniline into a 1L reaction bottle, heating to 140 ℃ in nitrogen atmosphere, reacting for 12h, monitoring the reaction completion in a liquid phase, washing twice with water, filtering, pulping twice with ethanol, and drying to obtain the intermediate b 48.36g, wherein the yield is 89%;
(3) adding the intermediate b (43.47g, 120mmol), sodium hydride (3.17g, 132mmol) and 250mL of Tetrahydrofuran (THF) into a 500mL reaction bottle, stirring at 0 ℃ for 8 minutes under the nitrogen atmosphere, slowly adding p-toluenesulfonic acid (27.45g, 144mmol) into the reaction solution by using a dropping funnel, naturally heating the reaction solution to room temperature, slowly adding water to quench the reaction after overnight, adding ethyl acetate to extract, separating, concentrating and drying to obtain 54.54g of an intermediate c with the yield of 88%;
(4) adding the intermediate c (51.65g, 100mmol), [1,1':3', 1' -terphenyl ] -5' -amine (24.53g, 100mmol), tris (dibenzylideneacetone) dipalladium (2.75g, 3mmol), tri-tert-butylphosphine (1.21g, 6mmol), sodium tert-butoxide (19.22g, 200mmol) and 500ml toluene into a 1L reaction flask, heating to 110 ℃ in a nitrogen atmosphere, reacting for 12h, monitoring the reaction completion of a liquid phase, cooling, adding 4-bromo-1, 1' -biphenyl (23.31g, 100mmol), heating to 110 ℃ and continuing to react for 8h, monitoring the reaction completion of the liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate and drying to obtain an intermediate e 56.65g and yield of 68%;
(5) adding the intermediate e (49.98g, 60mmol), sodium hydroxide (4.8g,120mmol) and 300ml of ethanol into a 500ml reaction bottle, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, monitoring the reaction completion of a liquid phase, cooling to room temperature, concentrating, washing with water and drying to obtain an intermediate f 39.10g, wherein the yield is 96%;
(6) a500 ml reaction flask was charged with intermediate f (33.94g, 50mmol), 4-isopropylbromobenzene (9.95g, 50mmol), tris (dibenzylideneacetone) dipalladium (1.37g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3mmol), sodium tert-butoxide (9.61g, 100mmol), 250ml of toluene, and the reaction was allowed to proceed at 110 ℃ for 12 hours under nitrogen atmosphere, followed by completion of the liquid phase monitoring reaction, cooling to room temperature, washing with water, filtration, slurrying with ethyl acetate, and drying to obtain 34.67g of the final product with a yield of 87%.
The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 797.0575, theoretical molecular weight 797.0580; call for C60H48N2(％):C 90.42,H 6.07,N 3.51Found:C 90.45,H 6.05,N 3.50。
Example 2
The compound (29) of the present invention can be synthesized by the following method.
Figure BDA0001626958080000191
(1) In the above (2) and (3), the intermediates a, b and c were synthesized in the same manner as in example 1;
(4) adding the intermediate c (51.65g, 100mmol), naphthalene-2-amine (14.32g, 100mmol), tris (dibenzylideneacetone) dipalladium (2.75g, 3mmol), tri-tert-butylphosphine (1.21g, 6mmol), sodium tert-butoxide (19.22g, 200mmol) and 500ml of toluene into a 1L reaction flask, heating to 110 ℃ in a nitrogen atmosphere for reaction for 12h, monitoring the reaction completion in a liquid phase, cooling, adding 2-bromonaphthalene (20.71g, 100mmol), heating to 110 ℃ for continuous reaction for 8h, monitoring the reaction completion in the liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain the intermediate e 49.34g with a yield of 70%;
(5) adding the intermediate e (42.29g, 60mmol), sodium hydroxide (4.8g,120mmol) and 300ml of ethanol into a 500ml reaction bottle, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, monitoring the reaction completion of a liquid phase, cooling to room temperature, concentrating, washing with water and drying to obtain 32.05g of an intermediate f with a yield of 97%;
(6) adding the intermediate f (27.54g, 50mmol), bromobenzene (7.85g, 50mmol), tris (dibenzylideneacetone) dipalladium (1.37g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3mmol), sodium tert-butoxide (9.61g, 100mmol) and 250ml toluene into a 500ml reaction flask, heating to 110 ℃ in a nitrogen atmosphere for 12h reaction, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain the final product g 27.58g with 88% yield.
The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 626.8035, theoretical molecular weight 626.8030; call for C47H34N2(％):C 90.06,H 5.47,N 4.47Found:C 90.08,H 5.46,N 4.46。
Example 3
The compound (40) of the present invention can be synthesized by the following method.
Figure BDA0001626958080000201
(1) In the above (2) and (3), the intermediates a, b and c were synthesized in the same manner as in example 1;
(4) adding the intermediate c (51.65g, 100mmol), dibenzothiophene-1-amine (19.93g, 100mmol), tris (dibenzylideneacetone) dipalladium (2.75g, 3mmol), tri-tert-butylphosphine (1.21g, 6mmol), sodium tert-butoxide (19.22g, 200mmol) and 500ml of toluene into a 1L reaction flask, heating to 110 ℃ in a nitrogen atmosphere, reacting for 12h, monitoring the reaction completion in a liquid phase, cooling, adding 2-bromonaphthalene (20.71g, 100mmol), heating to 110 ℃, continuing to react for 8h, monitoring the reaction completion in the liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain 50.22g of the intermediate e with a yield of 66%;
(5) adding the intermediate e (45.66g, 60mmol), sodium hydroxide (4.8g,120mmol) and 300ml of ethanol into a 500ml reaction bottle, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, concentrating, washing with water and drying to obtain an intermediate f 34.22g with a yield of 94%;
(6) a500 ml reaction flask was charged with intermediate f (30.34g, 50mmol), 4-tert-butylbromobenzene (10.66g, 50mmol), tris (dibenzylideneacetone) dipalladium (1.37g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3mmol), sodium tert-butoxide (9.61g, 100mmol), 250ml of toluene, and the reaction was allowed to warm to 110 ℃ for 12h under nitrogen atmosphere, followed by monitoring the completion of the reaction in the liquid phase, cooling to room temperature, washing with water, filtration, slurrying with ethyl acetate, and drying to obtain the final product g 31.04g, 84% yield.
The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 738.9928, theoretical molecular weight 738.9930; call for C53H42N2(％):C 86.14,H 5.73,N 3.79Found:C 86.12,H 5.74,N 3.80。
Example 4
The compound (50) of the present invention can be synthesized by the following method.
Figure BDA0001626958080000211
(1) In the above (2) and (3), the intermediates a, b and c were synthesized in the same manner as in example 1;
(4) adding the intermediate c (51.65g, 100mmol), naphthalene-2-amine (14.32g, 100mmol), tris (dibenzylideneacetone) dipalladium (2.75g, 3mmol), tri-tert-butylphosphine (1.21g, 6mmol), sodium tert-butoxide (19.22g, 200mmol) and 500ml of toluene into a 1L reaction flask, heating to 110 ℃ in a nitrogen atmosphere for reaction for 12h, monitoring the reaction completion in a liquid phase, cooling, adding 3-bromo-9, 9' -spirobifluorene (39.53g, 100mmol), heating to 110 ℃ for continuous reaction for 8h, monitoring the reaction completion in the liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain the intermediate e58.05g with a yield of 65%;
(5) adding the intermediate e (53.58g, 60mmol), sodium hydroxide (4.8g,120mmol) and 300ml of ethanol into a 500ml reaction bottle, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, concentrating, washing with water and drying to obtain an intermediate f 40.79g with a yield of 92%;
(6) adding the intermediate f (36.95g, 50mmol), bromobenzene (7.85g, 50mmol), tris (dibenzylideneacetone) dipalladium (1.37g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3mmol), sodium tert-butoxide (9.61g, 100mmol) and 250ml toluene into a 500ml reaction flask, heating to 110 ℃ in nitrogen atmosphere, reacting for 12h, monitoring the reaction completion in liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain the final product g 33.82g with the yield of 83%.
The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 815.0324, theoretical molecular weight 815.0320; call for C62H42N2(％):C 91.37,H 5.19,N 3.44Found:C 91.35,H 5.20,N 3.45。
Example 5
The compound (67) of the present invention can be synthesized by the following method.
Figure BDA0001626958080000221
(1) In the above (2) and (3), the intermediates a, b and c were synthesized in the same manner as in example 1;
(4) adding the intermediate c (51.65g, 100mmol), 9-phenyl-9H-carbazole-2-amine (25.83g, 100mmol), tris (dibenzylideneacetone) dipalladium (2.75g, 3mmol), tri-tert-butylphosphine (1.21g, 6mmol), sodium tert-butoxide (19.22g, 200mmol) and 500ml of toluene into a 1L reaction flask, heating to 110 ℃ in a nitrogen atmosphere, reacting for 12H, monitoring the reaction completion of a liquid phase, cooling, adding 1-bromodibenzofuran (24.71g, 100mmol), heating to 110 ℃, continuing to react for 8H, monitoring the reaction completion of the liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain an intermediate e 54.18g with a yield of 63%;
(5) adding the intermediate e (51.60g, 60mmol), sodium hydroxide (4.8g,120mmol) and 300ml of ethanol into a 500ml reaction bottle, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, concentrating, washing with water and drying to obtain an intermediate f 40.23g with a yield of 95%;
(6) adding the intermediate f (35.29g, 50mmol), bromobenzene (7.85g, 50mmol), tris (dibenzylideneacetone) dipalladium (1.37g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3mmol), sodium tert-butoxide (9.61g, 100mmol) and 250ml toluene into a 500ml reaction flask, heating to 110 ℃ in nitrogen atmosphere, reacting for 12h, monitoring the reaction completion in liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain the final product g 33.23g with yield of 85%.
The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 781.9593, theoretical molecular weight 781.9590; call for C57H39N3(％):C 87.55,H 5.03,N 5.37Found:C 87.56,H 5.04,N 5.35。
Example 6
The compound (88) of the present invention can be synthesized by the following method.
Figure BDA0001626958080000231
(1) In the above (2) and (3), the intermediates a, b and c were synthesized in the same manner as in example 1;
(4) adding the intermediate c (51.65g, 100mmol), dibenzofuran-1-amine (18.32g, 100mmol), tris (dibenzylideneacetone) dipalladium (2.75g, 3mmol), tri-tert-butylphosphine (1.21g, 6mmol), sodium tert-butoxide (19.22g, 200mmol) and 500ml of toluene into a 1L reaction flask, heating to 110 ℃ in a nitrogen atmosphere, reacting for 12h, monitoring the reaction completion of a liquid phase, cooling, adding 3-bromo-1, 1' -biphenyl (23.31g, 100mmol), heating to 110 ℃, continuing to react for 8h, monitoring the reaction completion of the liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain an intermediate e 51.65g with a yield of 67%;
(5) adding the intermediate e (46.26g, 60mmol), sodium hydroxide (4.8g,120mmol) and 300ml of ethanol into a 500ml reaction bottle, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, concentrating, washing with water and drying to obtain intermediate f 35.53g, wherein the yield is 96%;
(6) adding the intermediate f (30.84g, 50mmol), 3-bromo-1, 1' -biphenyl (11.66g, 50mmol), tris (dibenzylideneacetone) dipalladium (1.37g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3mmol), sodium tert-butoxide (9.61g, 100mmol) and 250ml toluene into a 500ml reaction flask, heating to 110 ℃ in a nitrogen atmosphere, reacting for 12h, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain the final product g 32.68g, wherein the yield is 85%.
The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 768.9605, theoretical molecular weight 768.9600; call for C57H40N2(％):C 89.03,H 5.24,N 3.64Found:C 89.00,H 5.25,N 3.65。
Example 7
The compound (146) of the present invention can be synthesized by the following method.
Figure BDA0001626958080000241
(1) In the above (2) and (3), the intermediates a, b and c were synthesized in the same manner as in example 1;
(4) adding the intermediate c (51.65g, 100mmol), 9-dimethyl-9H-fluorene-2-amine (20.93g, 100mmol), tris (dibenzylideneacetone) dipalladium (2.75g, 3mmol), tri-tert-butylphosphine (1.21g, 6mmol), sodium tert-butoxide (19.22g, 200mmol) and 500ml of toluene into a 1L reaction flask, heating to 110 ℃ in a nitrogen atmosphere, reacting for 12H, monitoring the reaction completion of a liquid phase, cooling, adding 1-bromodibenzofuran (24.71g, 100mmol), heating to 110 ℃, continuing to react for 8H, monitoring the reaction completion of the liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain an intermediate e 51.09g and a yield of 63%;
(5) adding the intermediate e (48.66g, 60mmol), sodium hydroxide (4.8g,120mmol) and 300ml of ethanol into a 500ml reaction bottle, heating to 80 ℃ in a nitrogen atmosphere, reacting for 2 hours, monitoring the completion of the reaction by a liquid phase, cooling to room temperature, concentrating, washing with water and drying to obtain an intermediate f 36.65g with a yield of 93%;
(6) adding the intermediate f (32.84g, 50mmol), 2-bromonaphthalene (10.35g, 50mmol), tris (dibenzylideneacetone) dipalladium (1.37g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3mmol), sodium tert-butoxide (9.61g, 100mmol) and 250ml of toluene into a 500ml reaction flask, heating to 110 ℃ in a nitrogen atmosphere, reacting for 12h, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, washing with water, filtering, pulping with ethyl acetate, and drying to obtain the final product g 33.54g with the yield of 82%.
The compounds were characterized as follows: mass spectrometer MALDI-TOF-MS (m/z) ═ 782.9866, theoretical molecular weight 782.9870; call for C58H42N2(％):C 88.97,H 5.41,N 3.58Found:C 88.95,H 5.42,N 3.58。
The preparation of compounds 1-153 can be accomplished as described in the preparation examples of compound samples above.
The hole transport layer, the electron blocking layer and the light extraction layer of the organic electroluminescent device of the present invention and the organic electroluminescent device prepared therefrom are explained below.
The organic light-emitting device is formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a cathode and a light-emitting layer. When the amine derivative of fluorenocarbazole is used as a hole transport material, an electron blocking material or a light emitting layer material, lower driving voltage, higher luminous brightness and higher current efficiency can be obtained, and the performance of an organic electroluminescent device is obviously improved. The technical effects of the compounds of the present invention will be described in more detail below by way of application examples.
The preparation of the devices 1 to 7 is carried out by taking the amine derivatives of fluorenocarbazole provided by the invention as hole transport materials, and the specific preparation method is as follows:
under the condition of high vacuum, evaporating tri [ 2-naphthyl phenylamino ] with the thickness of 20nm on an Indium Tin Oxide (ITO) glass substrate which is sequentially cleaned by a cleaning agent and deionized water through ultrasonic waves]Triphenylamine (2TNATA) is used as a hole injection layer, 40nm amine derivatives of the fluorenocarbazole provided by the invention are used as a hole transport layer, and 3% -10% of bis (4, 6-difluorophenylpyridine-N, C) is doped at 30nm2) 4,4 '-bis (2, 2-distyryl) -1,1' -biphenyl (DPVBI) of iridium picolinate (FIrpi) as the light-emitting layer, 40nm of 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) as the electron-transporting layer, 1nm of lithium fluoride (LiF) as the electron-injecting layer, and 120nm of aluminum (Al) as the metal cathode.
Device example 1:
ITO/2TNATA (20 nm)/compound 8(40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
Device example 2:
ITO/2TNATA (20 nm)/compound 29(40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
Device example 3:
ITO/2TNATA (20 nm)/compound 40(40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
Device example 4:
ITO/2TNATA (20 nm)/compound 50(40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
Device example 5:
ITO/2TNATA (20 nm)/compound 67(40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
Device example 6:
ITO/2TNATA (20 nm)/compound 88(40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
Device example 7:
ITO/2TNATA (20 nm)/compound 146(40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
The preparation of the device 8 and the device 9 by taking the amine derivative of fluorenocarbazole provided by the invention as an electron barrier layer material is specifically as follows:
under the condition of high vacuum, evaporating tri [ 2-naphthyl phenylamino ] with the thickness of 20nm on an Indium Tin Oxide (ITO) glass substrate which is sequentially cleaned by a cleaning agent and deionized water through ultrasonic waves]Triphenylamine (2TNATA) is used as a hole injection layer, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) with the particle size of 40nm is used as a hole transport layer, amine of fluorenocarbazole provided by the invention with the particle size of 20nm is used as an electron barrier layer material, and bis (4, 6-difluorophenylpyridine-N, C) with the particle size of 3-10% is doped with the particle size of 30nm2) 4,4 '-bis (2, 2-distyryl) -1,1' -biphenyl (DPVBI) of iridium picolinate (FIrpi) as the light-emitting layer, 40nm of 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) as the electron-transporting layer, 1nm of lithium fluoride (LiF) as the electron-injecting layer, and 120nm of aluminum (Al) as the metal cathode.
Device example 8:
ITO/2TNATA (20nm)/NPB (40 nm)/Compound 67(20 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
Device example 9:
ITO/2TNATA (20nm)/NPB (40 nm)/Compound 88(20 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm).
The preparation of the device 10 and the device 11 is carried out by taking the amine derivative of fluorenocarbazole provided by the invention as a light-emitting layer material, and the specific preparation method comprises the following steps:
under the condition of high vacuum, evaporating tri [ 2-naphthyl phenylamino ] with the thickness of 20nm on an Indium Tin Oxide (ITO) glass substrate which is sequentially cleaned by a cleaning agent and deionized water through ultrasonic waves]Triphenylamine (2TNATA) as a hole injection layer, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) at 40nm as a hole transport layer, and bis (4, 6-difluorophenylpyridine-N, C) doped 3% -10% at 30nm2) 4,4 '-bis (2, 2-distyryl) -1,1' -biphenyl (DPVBI) of iridium picolinate (FIrpic) as a light-emitting layer, 1,3,5 at 40nm-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) as the electron transport layer, 1nm lithium fluoride (LiF) as the electron injection layer, and 120nm aluminum (Al) as the metal cathode, 30nm of the amine derivative of fluorenocarbazole provided by the present invention as the light extraction layer material.
Device example 10:
ITO/2TNATA (20nm)/NPB (40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm)/Compound 67.
Device example 11:
ITO/2TNATA (20nm)/NPB (40 nm)/DPVBi: 5% wt FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120 nm)/Compound 88.
The preparation of device 12 without using the amine derivative of fluorenocarbazole provided by the present invention is specifically as follows:
under the condition of high vacuum, evaporating tri [ 2-naphthyl phenylamino ] with the thickness of 20nm on an Indium Tin Oxide (ITO) glass substrate which is sequentially cleaned by a cleaning agent and deionized water through ultrasonic waves]Triphenylamine (2TNATA) as a hole injection layer, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) at 40nm as a hole transport layer, and bis (4, 6-difluorophenylpyridine-N, C) doped 3% -10% at 30nm2) 4,4 '-bis (2, 2-distyryl) -1,1' -biphenyl (DPVBI) of iridium picolinate (FIrpi) as the light-emitting layer, 40nm of 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) as the electron-transporting layer, 1nm of lithium fluoride (LiF) as the electron-injecting layer, and 120nm of aluminum (Al) as the metal cathode.
Device example 12:
ITO/2TNATA(20nm)/NPB(40nm)/DPVBi：5％wt FIrpic(30nm)/TPBi(40nm)/LiF(1nm)/Al(120nm)。
the performance of the organic electroluminescent device was tested, and the results of the performance testing are shown in table 1 below.
TABLE 1 results of testing the performance of each device
Figure BDA0001626958080000281
Figure BDA0001626958080000291
It can be seen from the table that, compared with the conventional device, the device prepared by using the amine derivative of fluorenocarbazole provided by the invention as the hole transport material has the advantages that the starting voltage, the luminous brightness, the current efficiency, the lumen efficiency, the external quantum efficiency and the thermal decomposition temperature are obviously improved, the device is an ideal hole transport material, and can be independently used as a hole blocking material to effectively improve the performance of the device in the aspects of luminous brightness, the current efficiency, the lumen efficiency, the external quantum efficiency and the like, and also can be independently used as a light emitting layer material to effectively improve the performance of the device in the aspects of luminous brightness, the lumen efficiency and the like.
As shown in FIG. 1, the ratio of ITO/2TNATA (20 nm)/compound 67(40 nm)/DPVBi: the energy level diagram of the device prepared by taking 5 wt% FIrpic (30nm)/TPBi (40nm)/LiF (1nm)/Al (120nm) as the structure shows that the energy gaps among the functional layers of the device prepared by the structure are narrow, and the energy consumption and the recombination degree during the transition of carriers are effectively reduced. As shown in figures 2 and 3, the compound provided by the invention is used as a hole transport material, compared with the traditional hole transport material NPB, the amine derivative of fluorenocarbazole provided by the invention is an asymmetric compound with larger steric hindrance, and an intramolecular twisted pi conjugated system and a cross-linked structure effectively improve the local aggregation problem caused by excessive joule heat generated at the interface of an anode and a hole transport layer in the continuous working process of a device, so that the starting voltage of the device is low to 2.96V, and the luminous brightness is as high as 30060cd/m2The current efficiency is as high as 70.12 cd/A. As shown in fig. 4, when the compound provided by the present invention is used as a hole transport material, compared with a conventional hole transport material NPB, the amine derivative of fluorenocarbazole provided by the present invention has excellent charge injection and transport properties, effectively improves the problem of exciton annihilation caused by the recombination of electrons and holes in a non-light emitting layer, and has an external quantum efficiency as high as 19.37%.
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 (5)

1. The amine derivative of fluorenocarbazole is characterized in that the structural general formula is as follows:
Figure FDA0002897940980000011
the R is1And R2Is any one of the following groups:
Figure FDA0002897940980000012
the other of R1 and R2 is any one of the following groups:
Figure FDA0002897940980000021
wherein, is the site linked to N on the amine group;
the R is3Any one of the following groups, unsubstituted or substituted with an alkyl group:
Figure FDA0002897940980000022
wherein, is a site linked to N on the carbazole;
the R is1、R2And R3The same or different.
2. The amine derivative of fluorenocarbazole according to claim 1, characterized in that the structures of R1 and R2 are as follows:
Figure FDA0002897940980000031
wherein x is the site attached to N on the amine group.
3. A process for the preparation of amine derivatives of fluorenocarbazole as claimed in claim 1 or 2, characterized in that it comprises the following scheme:
Figure FDA0002897940980000041
4. use of the amine derivative of fluorenocarbazole according to claim 1 or 2 for the production of organic electroluminescent devices, organic solar cells, organic thin-film transistors, organic light-emitting transistors and/or organic field-effect transistors.
5. An organic electroluminescent device, which is formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode, or formed by sequentially stacking a glass substrate, an anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer, a cathode and a light emitting layer, characterized in that the hole transport layer, the electron blocking layer, the luminescent layer and/or the light emitting layer at least comprise the amine derivative of fluorenocarbazole according to claim 1 or 2.
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