CN110128323B - Fluorenocarbazole derivative, and preparation method and application thereof - Google Patents

Fluorenocarbazole derivative, and preparation method and application thereof Download PDF

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CN110128323B
CN110128323B CN201910176988.XA CN201910176988A CN110128323B CN 110128323 B CN110128323 B CN 110128323B CN 201910176988 A CN201910176988 A CN 201910176988A CN 110128323 B CN110128323 B CN 110128323B
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fluorenocarbazole
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穆广园
庄少卿
任春婷
徐鹏
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Wuhan Shangsai Optoelectronics Technology Co ltd
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Abstract

The invention belongs to the technical field of organic synthesis, particularly relates to the technical field of organic synthesis, and particularly relates to a fluorenocarbazole derivative and a preparation method and application thereof. The fluorenocarbazole derivative provided by the invention is a hole transport material and a luminescent layer main body material with excellent comprehensive performances such as electroluminescence, thermal stability, service life and the like, is simple to synthesize, has high yield and purity, and can meet the requirements on material performance and quality in industrial application.

Description

Fluorenocarbazole derivative, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a fluorenocarbazole derivative, and a preparation method and application thereof.
Background
Carbazole is an electron-rich nitrogen-containing heterocyclic compound, and electrophilic nitrogen atoms of carbazole absorb electrons on carbon-carbon double bonds through an induced effect and simultaneously have a P-pi conjugated effect, so that carbazole rings have high hole mobility and luminous efficiency, and derivatives of carbazole rings have potential wide application in fields such as photoelectric materials, dyes, medicines, supramolecular recognition and the like.
Due to the limitation of a molecular structure, the thermal stability of a single carbazole compound molecule is poor, and meanwhile, due to the fact that small molecule luminescent materials are easy to form agglomeration in a solid phase, fluorescence quenching occurs or red shift of emitted light is caused. Therefore, many researchers design carbazole rings into fused ring structures similar to pentacene so as to increase the plane rigid structure, and furthermore, groups such as triazine, carbazole, arylamine and the like are introduced to the easily modified 9-site atom to reduce the quenching of molecular agglomeration and improve the performances of the easily modified 9-site atom in the aspects of current efficiency, luminous efficiency, light color and brightness, so that some progress is made in the field at present, however, some problems still exist in carbazole polymer electroluminescent materials and devices, and while some indexes are optimized, other properties are deteriorated and cannot reach the commercial application level, such as: the designed compound has a high hole transport rate, the carrier electron-hole imbalance is caused by the huge transmission rate difference between the carrier and the electron transmission rate, and a carrier trap causes a certain degree of nonradiative transition; the rigid planar structure of the material expansion results in some degree of crystallization of the molecules when the device overheats. Therefore, the fine structure of the designed molecule must be developed from the light-emitting mechanism in order to optimize various performance indexes of the material.
In addition, the steric effect has a great influence on the synthesis of compounds, the 3, 6-positions of carbazole are activated by nitrogen atoms, and a plurality of electrophilic substitution reactions are easy to occur at the two positions, so that the 3,6, 9 positions of carbazole ring are easy to introduce other functional groups through chemical modification, and the synthesis of substitution at 1,2, 7, 8 positions of carbazole is much more difficult, thereby restricting the development of carbazole organic electroluminescent materials with more excellent performance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a fluorenocarbazole derivative, and a preparation method and application thereof. Through the fine design of the structure, the fluorenocarbazole derivative ensures the optimization of the driving voltage, the light color, the thermal stability, the luminous efficiency and the service life of the material in the working process of the device, particularly the light color, the thermal stability and the service life of the material, and avoids the problem that the improvement of the single performance of the photoelectric material cannot meet the current situation of industrial application. In addition, the fluorene carbazole derivative is prepared by taking halogenated aniline and halogenated fluorene derivatives as basic raw materials, carrying out SUZUKI reaction and ring-closing reaction under a mixed system of a specific catalyst, a ligand, alkali and a solvent to obtain fluorene carbazole, and carrying out Ullmann reaction and coupling reaction under the action of the specific catalyst, the ligand, the alkali and the solvent, wherein the synergistic effect of the specific catalyst, the ligand, the alkali and the solvent enables each step of synthesis to be efficiently reacted, the yield is over 80 percent, and the material can be purified by recrystallization and/or pulping, the purity of the material is over 99 percent, the synthesis is simple, the product yield and the purity are high, and the fluorene carbazole derivative is suitable for industrial production.
The technical scheme provided by the invention is as follows:
a fluorenocarbazole derivative has a structural general formula shown as the following formula (I):
Figure BDA0001989877910000021
wherein X is CH or CR0Or N, said R0Selected from cyano, nitro, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C6～45Aryloxy group of (A), C6～45Arylthio group of (a);
y is N or P ═ O;
R1、R2are each independently C6～45Aryl or C of3～45Heteroaryl of (A), R1And R2The same or different;
n is 1,2 or 3.
Specifically, the R is1Or R2C of (A)6～45Is selected from: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthylphenyl, substituted or unsubstituted anthrylphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenylnaphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl; the R is1Or R2C of (A)3～45The heteroaryl group of (a) is selected from: substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl.
Specifically, the fluorenocarbazole derivative includes compounds represented by chemical formulas 1 to 192:
Figure BDA0001989877910000022
Figure BDA0001989877910000031
Figure BDA0001989877910000041
Figure BDA0001989877910000051
Figure BDA0001989877910000061
Figure BDA0001989877910000071
Figure BDA0001989877910000081
Figure BDA0001989877910000091
Figure BDA0001989877910000101
Figure BDA0001989877910000111
Figure BDA0001989877910000121
the invention also provides a preparation method of the fluorenocarbazole derivative, which comprises the following steps:
s1, carrying out SUZUKI reaction on 4-bromo-9, 9-dimethyl-9H-fluorene shown in formula (a) and X hetero 2-chloroaniline shown in formula (b) in the presence of a mixed system T1 of a metal catalyst, a ligand, alkali and a solvent to obtain X hetero N- (2-chlorophenyl) -9, 9-dimethyl-9H-fluorene-4-amine shown in formula (c);
s2: carrying out ring-closure reaction on X hetero N- (2-chlorphenyl) -9, 9-dimethyl-9H-fluorene-4-amine shown in the formula (c) in the presence of a mixed system T2 of a metal catalyst, a ligand, alkali and a solvent to obtain X hetero fluorene carbazole shown in the formula (d);
s3: carrying out Ullmann reaction on X heterofluorenocarbazole shown in formula (d) and halogenated compound shown in formula (e) in the presence of a mixed system T3 of a metal catalyst, a ligand, alkali and a solvent to obtain a compound shown in formula (f);
s4: carrying out coupling reaction on a compound shown in a formula (f) and a compound shown in a formula (g) in the presence of a mixed system T4 of a metal catalyst, a ligand, alkali and a solvent to obtain a fluorenocarbazole derivative shown in a formula (I);
Figure BDA0001989877910000131
specifically, the catalysts in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 are respectively and independently selected from: at least one of tris (dibenzylideneacetone) dipalladium, palladium acetate, tetrakis (triphenylphosphine) palladium, cuprous iodide, [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium.
Specifically, the ligands in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 are respectively and independently selected from: triphenylphosphine, tricyclohexylphosphine, 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, tri-tert-butylphosphine tetrafluoroborate and 18-crown-6; the alkali existing in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 is respectively and independently selected from the following group: sodium tert-butoxide, cesium carbonate, potassium carbonate and sodium carbonate.
Specifically, the solvents in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 are respectively and independently selected from: at least one of toluene, xylene, N-methylpyrrolidone, ethanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, and water.
Preferably, the catalyst of the mixed system T1 is tris (dibenzylideneacetone) dipalladium, the ligand is triphenylphosphine or 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl, the base is potassium carbonate or sodium tert-butoxide, and the solvent is ethanol and water.
Preferably, the catalyst of the mixed system T2 is palladium acetate, the ligand is tricyclohexylphosphine or tri-tert-butylphosphine tetrafluoroborate, the base is potassium carbonate or cesium carbonate, and the solvent is N, N-dimethylformamide or N-methylpyrrolidone.
Preferably, the catalyst of the mixed system T3 is cuprous iodide, the ligand is 18-crown-6, the base is potassium carbonate, and the solvent is xylene or N, N-dimethylacetamide.
Preferably, the catalyst of the mixed system T4 is tris (dibenzylideneacetone) dipalladium, the ligand is tri-tert-butylphosphine tetrafluoroborate, the base is sodium tert-butoxide, and the solvent is toluene.
Specifically, in step S1, the material is prepared according to the formula (a) of 4-bromo-9, 9-dimethyl-9H-fluorene, the formula (b) of X hetero 2-chloroaniline, the formula (b) of metal catalyst, the formula (b) of ligand, the formula (b) of alkali, and the formula (b) of solvent, wherein the ratio of the solvent to the material is 1 mmol: 1.0-1.5 mmol: 0.005-0.02 mmol: 0.005-0.02 mmol: 2-4 mmol:2-10mL of the mixed system T1.
Specifically, in step S2, the material is X hetero N- (2-chlorophenyl) -9, 9-dimethyl-9H-fluoren-4-amine represented by formula (c): metal catalyst: ligand: alkali: the solvent is 1 mmol: 0.02-0.2mmol:0.01-0.3mmol:2-5mmol:2-10mL of the mixed system T2.
Specifically, in step S3, each material is X heterofluorenocarbazole represented by formula (d): a halogenated compound represented by formula (e): metal catalyst: ligand: alkali: the solvent is 1 mmol: 1-3 mmol: 0.1-0.5 mmol: 0.1-0.5 mmol:2-5mmol:2-10mL of the mixed system T3.
Specifically, in step S4, the compounds represented by formula (f) are fed: a compound represented by the formula (g): metal catalyst: ligand: alkali: the solvent is 1 mmol: 1-3 mmol: 0.005-0.02 mmol: 0.01-0.04 mmol: 2-4 mmol:2-10mL of the mixed system T4.
Specifically, the temperature of the mixed system T1 was controlled at 60 to 80 ℃ when the SUZUKI reaction was performed in step S1.
Specifically, the temperature of the mixed system T2 during the ring closure reaction in the step S2 is controlled at 140-165 ℃.
Specifically, the temperature of the mixed system T2 was controlled at 140 ℃ and 165 ℃ during the Ullmann reaction in step S3.
Specifically, the temperature of the mixed system T2 is controlled to 90-115 ℃ when the coupling reaction is carried out in the step S4.
The invention also provides an electronic element which comprises two electrodes, and a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer which are positioned between the two electrodes, wherein the hole transport layer and/or the light-emitting layer are/is composed of the fluorenocarbazole derivative.
Specifically, the light-emitting layer is formed by doping a light-emitting layer host material and a light-emitting layer guest material, and the light-emitting layer host material is composed of the fluorenocarbazole derivative.
The invention gives full play to the characteristic of wide energy gap of a rigid plane biphenyl structure, and forms a fluorene carbazole unit with built-up outer branches in a molecule by condensing the 1,2 position of 9H-carbazole and the 3,4 position of 9, 9-dimethyl-9H-fluorene, and then forms a novel fluorene carbazole derivative with excellent comprehensive electroluminescence characteristics by using an aromatic amine compound with a large conjugation system of a benzene ring, particularly a biphenyl structure bridging branch, on an easily modified nitrogen site. Compared with the thickening of other functional groups with rigid plane biphenyl structures and the thickening of other sites, the thickening of the 1, 2-position of 9H-carbazole and the 3, 4-position of 9, 9-dimethyl-9H-fluorene enables the 9-position electron-pushing group of carbazole and doped nitrogen atom to adjust the electron cloud density of 1, 2-position extended conjugated structure, the conjugation degree is enhanced, the thermal stability is improved, in addition, the 9-position double methyl structure of fluorene avoids the aggregation effect of materials among molecules, and solves the problems of aggregation crystallization and close packing among molecules caused by heat accumulation of materials in device application. Furthermore, on the nitrogen site which is easy to modify by the fluorenocarbazole unit, the aromatic amine structure is bridged by a benzene ring, particularly a biphenyl structure to form a linear aromatic amine fluorenocarbazole derivative, the fluorene carbazole unit with a branched chain structure avoids the easy crystallization characteristic of the linear aromatic amine structure, the linear connection of triarylamine is fully utilized to improve the glass transition temperature of the material, and the fluorene carbazole derivative is a hole transport material with remarkable thermal stability, non-crystallization characteristic and film forming characteristic. In addition, the long conjugated chain of the biphenyl structure enables the HOMO and LUMO energy levels to be distributed in two different structural units, the energy gap is widened, the hole injection energy barrier is reduced, non-radiative transition of electrons across a luminescent layer in a hole transport layer is prevented, the luminous efficiency is improved, in addition, the electroluminescent characteristic blue shift is realized by further introducing a fluorene structure in a fluorene carbazole structure constructed by a blue light chromophore of fluorene and an arylamine structure, the fluorene carbazole derivative has obvious application effects in a deep blue light electroluminescent device, and the fluorene carbazole derivative is a luminescent layer main body material with excellent comprehensive performances such as light color, thermal stability, service life and the like.
In addition, the fine design of the synthesis path comprises the selection of raw materials, the optimized matching of a catalyst, a ligand, alkali and a solvent and the simplified regulation and control of post-treatment, the yield of each step of the fluorenocarbazole derivative is maintained to be more than 80%, the purity of the fluorenocarbazole derivative reaches more than 99%, the requirements of an industrialized layer on material cost and purity are further met, and the method has a good industrial application prospect.
Drawings
FIG. 1 is a diagram of the energy levels of a device in which a compound (99) provided by the present invention is used as a hole transport layer;
FIG. 2 is a diagram of the energy level of a device in which the compound (99) provided by the present invention is used as a light emitting layer;
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 (1)
Synthesis of fluorenocarbazole:
Figure BDA0001989877910000151
s1, putting 4-bromo-9, 9-dimethyl-9H-fluorene (8.20g, 30 mmol), 2-chloroaniline (4.59g, 36mmol), triphenylphosphine (0.04g, 0.15mmol) and sodium tert-butoxide (8.65g, 90mmol) into a 250mL three-necked flask, adding 80mL ethanol and 40mL water, adding tris (dibenzylideneacetone) dipalladium (0.27g, 0.3mmol) under nitrogen atmosphere, reacting at 70 ℃ for 1-4H, monitoring the completion of the reaction of 4-bromo-9, 9-dimethyl-9H-fluorene by liquid phase monitoring, adding water for quenching reaction, separating, concentrating the organic phase, leaching silica gel column with petroleum ether, concentrating the leacheate to obtain 9.02g of colorless transparent oily N- (2-chlorophenyl) -9, 9-dimethyl-9H-fluorene-4-amine, the yield is 94 percent, and the purity is 99.85 percent.
S2, putting the N- (2-chlorphenyl) -9, 9-dimethyl-9H-fluorene-4-amine (5.67g, 20mmol), tri-tert-butylphosphine tetrafluoroborate (0.06g, 0.2mmol) and potassium carbonate (11.05g, 80mmol) into a 100mL three-necked bottle, adding 40mL N-methylpyrrolidone, adding palladium acetate (0.09g, 0.4mmol) under nitrogen atmosphere, reacting at 160 ℃ for 1-4H, monitoring the reaction completion of a liquid phase, cooling to room temperature, washing with water, separating, concentrating an organic phase, leaching with a silica gel column through petroleum ether, concentrating with a leaching solution, and obtaining 5.04g of yellow powdery fluorenocarbazole with the yield of 89% and the purity of 99.32%.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Figure BDA0001989877910000161
Putting the fluorenocarbazole (2.83g, 10mmol), 4-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol), 18-crown-6 (0.26g, 1mmol) and potassium carbonate (5.53g, 40mmol) into a 100mL three-necked flask, adding 40mL dimethylacetamide, adding cuprous iodide (0.38 g, 2mmol) under nitrogen atmosphere, reacting at 165 ℃ for 4-8h, monitoring the reaction at liquid phase, cooling to room temperature, washing with water, filtering, thermally pulping the filter cake with 3-5 times of ethyl acetate, thermally pulping with a mixed solvent of ethyl acetate and ethanol of 10:1, to obtain 4.45g of white powdered 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole with a yield of 86%, the purity is 99.14%.
Synthesis of Compound (1)
Figure BDA0001989877910000162
Carbazole (2.57g, 5mmol), diphenylamine (1.69g, 10mmol), tri-tert-butylphosphine tetrafluoroborate (0.03g, 0.1mmol), sodium tert-butoxide (1.92g, 20mmol), 40mL of toluene was added, tris (dibenzylideneacetone) dipalladium (0.05g, 0.05mmol) was added under nitrogen atmosphere, reaction was carried out at 115 ℃ for 4-8h, and monitoring of 12- (4 '-bromo- [1,1' -biphenyl) was carried out in the liquid phase]-4-yl) -fluorenocarbazole, cooling to room temperature, washing with water, filtering, and filtering the filter cake with ethanol: the ethyl acetate was heated and beaten twice in a solvent of 5:1 to give 2.80g of the compound (1) as a white powder in 93% yield and 99.34% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 602.7812, theoretical molecular weight: 602.7810, respectively; call for C45H34N2(％):C 89.67,H 5.69,N 4.65,Found:C 89.65,H 5.70,N 4.65。
Example 2: synthesis of Compound (4)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole
Figure BDA0001989877910000171
By substituting 4-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol) in example 1 with 3-bromo-3 '-iodo-1, 1' -biphenyl (3.59g, 10mmol), and the same procedure as in 1b in example 1, 4.39g of 12- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole was obtained as a white powder in 85% yield and 99.09% purity.
Synthesis of Compound (4)
Figure BDA0001989877910000172
5mmol) to 12- (3 '-bromo- [1,1' -biphenyl]-3-yl) -fluorenocarbazole (2.57g, 5mmol) and the other synthetic procedures were the same as in 1c of example 1 to give 2.75g of compound (4) as a white powder in 91% yield and 99.18% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 602.7805, theoretical molecular weight: 602.7810, respectively; call for C45H34N2(％):C 89.67,H 5.69,N 4.65,Found:C 89.66,H 5.70,N 4.64。
Example 3: synthesis of Compound (6)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (3 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Figure BDA0001989877910000173
By substituting 4-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol) in example 1 with 3-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol), and the other synthetic procedures in the same manner as in 1b in example 1, 4.33g of 12- (3 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole was obtained as a white powder in 84% yield and 99.10% purity.
Figure RE-GDA0002101616650000181
The 12- (4 '-bromo- [1,1' -biphenyl) of example 1 was reacted]-4-Yl-Fluorenocarbazole (2.57g, 5mmol) to 12- (3 '-bromo- [1,1' -biphenyl]-4-Yl-Fluorenocarbazole (2.57g, 5mmol) and diphenylamine (1.69g, 10mmol) replaced by N-phenyl- [1,1' -Biphenyl]2.95g of compound (6) was obtained in the same manner as in 1c of example 1 in the same manner as for the synthesis of (2.45g, 10mmol) of (E) -4-amine (yield: 87%, purity: 99.10%). Mass spectrometerMALDI-TOF-MS (m/z) ═ 678.8786, theoretical molecular weight: 678.8790, respectively; call for C51H38N2(％):C 90.23,H 5.64,N 4.13, Found:C 90.25,H 5.63,N 4.12。
Example 4: synthesis of Compound (9)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Synthesis procedure was the same as that of 1b in example 1
Synthesis of Compound (9)
Figure BDA0001989877910000182
The diphenylamine (1.69g, 10mmol) in example 1 was replaced with N-phenyl- [1,1' -biphenyl ] -3-amine (2.45g, 10mmol), and the other synthetic procedures were the same as those of 1c in example 1, whereby 3.02g of the compound (9) was obtained as a white powder in a yield of 89% and a purity of 99.15%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 678.8786, theoretical molecular weight: 678.8790, respectively; call for C51H38N2(％):C 90.23,H 5.64,N 4.13,Found:C 90.24,H 5.64,N 4.12。
Example 5: synthesis of Compound (13)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Synthesis procedure was the same as that of 1b in example 1
Synthesis of Compound (13)
Figure BDA0001989877910000191
Amine (3.21g, 10mmol) and the other synthesis procedures were the same as those of 1c in example 1 to obtain white powderCompound (13)3.31g, yield 88%, purity 99.20%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 754.9776, theoretical molecular weight: 754.9770, respectively; call for C57H42N2(％):C 90.68,H 5.61,N 3.71,Found:C 90.70,H 5.60,N 3.70。
Example 6: synthesis of Compound (20)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole
The procedure was the same as that of example 2, 1b
Synthesis of Compound (20)
Figure BDA0001989877910000192
By substituting 12- (4' -bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with 12- (3' -bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole (2.57g, 5mmol), and substituting diphenylamine (1.69g, 10mmol) in example 2 with bis ([1,1' -biphenyl ] -3-yl) amine (3.21g, 10mmol), the other synthetic procedures were the same as those of 1c in example 1, 3.28g of compound (20) was obtained as a white powder in 87% yield and 99.10% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 754.9776, theoretical molecular weight: 754.9770, respectively; call for C57H42N2(％):C 90.68,H 5.61,N 3.71,Found:C 90.70,H 5.60,N 3.70。
Example 7: synthesis of Compound (27)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole
Figure BDA0001989877910000201
By substituting 4-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol) in example 1 with 4 '-bromo-3-iodo-1, 1' -biphenyl (3.59g, 10mmol), and following the same procedure as in 1b in example 1, 4.35g of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole was obtained as a white powder in 85% yield and 99.14% purity.
Synthesis of Compound (27)
Figure BDA0001989877910000202
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole (2.57g, 5mmol), and substituting diphenylamine (1.69g, 10mmol) in example 2 with 4- (naphthalen-1-yl) -N-phenylaniline (2.95g, 10mmol), the other synthetic procedures were the same as those of 1c in example 1, whereby 2.98g of compound (27) was obtained as a white powder in a yield of 82% and a purity of 99.08%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 728.9394, theoretical molecular weight: 728.9390, respectively; call for C55H40N2(％):C 90.63,H 5.53,N 3.84,Found:C 90.61,H 5.54,N 3.85。
Example 8: synthesis of Compound (33)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Synthesis procedure was the same as that of 1b in example 1
Figure BDA0001989877910000203
The procedure for the synthesis of 1c in example 1 was otherwise identical to the procedure for the synthesis of 1c in example 1 except that diphenylamine (1.69g, 10mmol) in example 1 was replaced with N-phenylnaphthalen-2-amine (2.19g, 10mmol), whereby 2.77g of compound (33) was obtained as a white powder in 85% yield and 99.16% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 652.8418, theoretical molecular weight: 652.8410, respectively; call for C49H36N2(％):C 90.15,H 5.56,N 4.29,Found:C 90.14,H 5.55,N 4.30。
Example 9: synthesis of Compound (45)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Synthesis procedure was the same as that of 1b in example 1
Synthesis of Compound (45)
Figure BDA0001989877910000211
The procedure of 1c in example 1 was otherwise identical to the procedure of 1.69g of diphenylamine (1.69g, 10mmol) in example 1 except that di-phenylamine (2.69g, 10mmol) was used instead of di-naphthalen-1-yl-amine, whereby 2.87g of compound (45) was obtained as a white powder in 82% yield and 99.02% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 702.9006, theoretical molecular weight: 702.9010, respectively; call for C53H38N2(％):C 90.57,H 5.45,N 3.99,Found:C 90.55,H 5.45,N 4.00。
Example 10: synthesis of Compound (56)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Synthesis procedure was the same as that of 1b in example 1
Synthesis of Compound (56)
Figure BDA0001989877910000212
The procedure of example 1c was repeated except for replacing diphenylamine (1.69g, 10mmol) in example 1 with 9, 9-dimethyl-N-phenyl-9H-fluoren-3-amine (2.85g, 10mmol), to give 2.98g of compound (56) as a white powder in 83% yield and 99.18% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 718.9435, theoretical molecular weight: 718.9440, respectively; call for C54H42N2(％):C 90.21,H 5.89,N 3.90,Found:C 90.20,H 5.90,N 3.90。
Example 11: synthesis of Compound (61)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole
Synthesis procedure was the same as that of 1b in example 1
Figure BDA0001989877910000222
The procedure of 1c in example 1 was otherwise identical to the procedure for the preparation of 1c in example 1 except that diphenylamine (1.69g, 10mmol) in example 1 was replaced with N-phenyldibenzofuran-4-amine (2.59g, 10mmol), whereby 2.83g of compound (61) was obtained as a white powder in 82% yield and 99.00% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 692.8622, theoretical molecular weight: 692.8620, respectively; call for C51H36N2(％):C 88.41,H 5.24,N 4.04,Found:C 88.40,H 5.26,N 4.05。
Example 12: synthesis of Compound (66)
Synthesis of fluorenocarbazole:
the procedure was the same as that of example 1a
Synthesis of 12- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -fluorenocarbazole
The procedure was the same as that of example 2, 1b
Synthesis of Compound (66)
Figure BDA0001989877910000221
The procedure of 1c in example 1 was otherwise identical to the procedure for the preparation of 1c in example 1 except that diphenylamine (1.69g, 10mmol) in example 1 was replaced with N-phenyldibenzothiophene-4-amine (2.75g, 10mmol), whereby 2.93g of compound (66) was obtained as a white powder in 83% yield and 99.08% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 708.9227, theoretical molecular weight: 708.9230, respectively; call for C51H36N2(％):C 86.41,H 5.12,N 3.95,Found:C 86.40,H 5.12,N 3.95。
Example 13: synthesis of Compound (69)
Synthesis of azafluorenocarbazoles:
Figure BDA0001989877910000231
by substituting 2-chloroaniline (4.59g, 36mmol) in example 1 with 3-chloro-2-aminopyridine (4.63g, 36mmol) and performing the same synthesis as in 1a in example 1, 8.69g of azafluorenocarbazole was obtained as a yellow powder in 85% yield and 99.26% purity.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
Figure BDA0001989877910000232
By substituting fluorenocarbazole (2.83g, 10mmol) in example 1 with azafluorenocarbazole (2.84g, 10mmol) and performing the same synthesis as in 1b in example 1, 4.43g of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole was obtained in the form of white powder with a yield of 86% and a purity of 99.10%.
Synthesis of Compound (69)
Figure BDA0001989877910000233
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), the same procedure as in example 1c in example 1 was repeated, whereby 2.80g of compound (69) was obtained as a white powder in a yield of 93% and a purity of 99.30%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 603.7695, theoretical molecular weight: 603.7690, respectively; call for C44H33N3(％):C 87.53,H 5.51,N 6.96,Found:C 87.55,H 5.50,N 6.96。
Example 14: synthesis of Compound (79)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 13.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
The procedure was the same as that for 1b in example 13.
Synthesis of Compound (79)
Figure BDA0001989877910000241
By substituting 12- (4' -bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4' -bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), diphenylamine (1.69g, 10mmol) with bis ([1,1' -biphenyl ] -3-yl) amine (3.21g, 10mmol), and by following the same procedure as in example 1c in example 1, 3.28g of compound (79) as a white powder was obtained in 87% yield and 99.25% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 755.9642, theoretical molecular weight: 755.9650, respectively; call for C56H41N3(％):C 88.97,H 5.47,N 5.56,Found:C 88.98,H 5.45,N 5.57。
Example 15: synthesis of Compound (92)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 13.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole
Figure BDA0001989877910000242
4.26g of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole was obtained as a white powder in the same manner as in 1b of example 1 except that 4-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol) in example 1 was replaced with 4 '-bromo-3-iodo-1, 1' -biphenyl (3.59g, 10mmol), and fluorenocarbazole (2.83g, 10mmol) was replaced with azafluorenocarbazole (2.84g, 10mmol), and the other synthesis procedures were the same as in 1b of example 1, whereby 83% yield and 99.08% purity were obtained.
Synthesis of Compound (92)
Figure BDA0001989877910000251
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole (2.58g, 5mmol), diphenylamine (1.69g, 10mmol) with di (naphthalen-2-yl) amine (2.69g, 10mmol), and the other synthetic procedures were the same as those in example 1c in example 1, 3.05g of compound (92) was obtained as a white powder in 87% yield and 99.20% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 703.8886, theoretical molecular weight: 703.8890, respectively; call for C52H37N3(％):C 88.73,H 5.30,N 5.97,Found:C 88.72,H 5.30,N 5.98。
Example 16: synthesis of Compound (99)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 13.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
The procedure was the same as for 1a in example 13.
Synthesis of Compound (99)
Figure BDA0001989877910000252
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), diphenylamine (1.69g, 10mmol) with 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine (2.85g, 10mmol), and by following the same procedure as in example 1c in example 1, 2.95g of compound (99) was obtained as a white powder in a yield of 82% and a purity of 99.04%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 719.9322, theoretical molecular weight: 719.9320, respectively; call for C53H41N3(％):C 88.42,H 5.74,N 5.84,Found:C 88.40,H 5.75,N 5.85。
Example 17: synthesis of Compound (107)
Synthesis of azafluorenocarbazoles:
Figure BDA0001989877910000261
by substituting 2-chloroaniline (4.59g, 36mmol) in example 1 with 3-amino-4-chloropyridine (4.63g, 36mmol) and performing the same synthesis as in 1a in example 1, 8.90g of azafluorenocarbazole was obtained as a yellow powder in 87% yield and 99.26% purity.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
Figure BDA0001989877910000262
By substituting fluorenocarbazole (2.83g, 10mmol) in example 1 with azafluorenocarbazole (2.84g, 10mmol) and performing the same synthesis as in 1b in example 1, 4.38g of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole was obtained as a white powder in 85% yield and 99.05% purity.
Figure BDA0001989877910000263
The procedure of example 1c of example 1 was otherwise identical except for replacing 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), whereby 2.83g of compound (107) was obtained as a white powder in 94% yield and 99.22% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 603.7688, theoretical molecular weight: 603.7690, respectively; call for C44H33N3(％):C 87.53,H 5.51,N 6.96,Found:C 87.54,H 5.50,N 6.96。
Example 18: synthesis of Compound (114)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 17.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
The procedure was the same as that for 1b in example 17.
Synthesis of Compound (114)
Figure BDA0001989877910000271
The procedure of example 1c was otherwise the same as that of example 1 except for replacing 12- (4' -bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with 12- (4' -bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), diphenylamine (1.69g, 10mmol) with bis ([1,1' -biphenyl ] -4-yl) amine (3.21g, 10mmol), whereby 3.34g of compound (114) was obtained as a white powder in 88% yield and 99.15% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 755.9654, theoretical molecular weight: 755.9650, respectively; call for C56H41N3(％):C 88.97,H 5.47,N 5.56,Found:C 88.96,H 5.46,N 5.58。
Example 19: synthesis of Compound (120)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 17.
Synthesis of 12- (3 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
Figure BDA0001989877910000272
By substituting 2.83g, 10mmol of fluorenocarbazole in example 1 with 2.84g, 10mmol of the azafluorenocarbazole and 3.59g, 10mmol of 4-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol) with 3-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol), a white powdery 12- (3 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole was obtained in an amount of 4.48g, a yield of 87%, and a purity of 99.16%, in the same manner as in 1b of example 1.
Figure BDA0001989877910000273
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (3 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), diphenylamine (1.69g, 10mmol) with 4- (naphthalen-1-yl) -N-phenylaniline (2.95g, 10mmol), and the other synthetic procedures were the same as those in example 1c in example 1, 3.06g of the compound (120) as a white powder was obtained, with a yield of 84% and a purity of 99.06%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 729.9264, theoretical molecular weight: 729.9270, respectively; call for C54H39N3(％):C 88.86,H 5.39,N 5.76,Found:C 88.85,H 5.40,N 5.75。
Example 20: synthesis of Compound (135)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 17.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
The procedure was the same as that for 1b in example 17.
Figure BDA0001989877910000281
5mmol) to 12- (4 '-bromo- [1,1' -biphenyl]2.88g of compound (135) as a white powder was obtained in 83% yield and 99.02% purity in the same manner as in example 1c in example 1 except that (2.58g, 5mmol) of (E) -4-azafluorenocarbazole and (1.69g, 10mmol) of diphenylamine were replaced with (2.59g, 10mmol) of N-phenyldibenzofuran-4-amine.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 693.8492, theoretical molecular weight: 693.8500, respectively; call for C50H35N3(％):C 86.55,H 5.08,N 6.06,Found:C 86.55,H 5.06,N 6.07。
Example 21: synthesis of Compound (139)
Synthesis of azafluorenocarbazoles:
Figure BDA0001989877910000282
by substituting 2-chloroaniline (4.59g, 36mmol) in example 1 with 4-amino-3-chloropyridine (4.63g, 36mmol) and performing the same synthesis as in 1a in example 1, 8.70g of azafluorenocarbazole was obtained as a yellow powder in 85% yield and 99.21% purity.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
Figure BDA0001989877910000291
By substituting fluorenocarbazole (2.83g, 10mmol) in example 1 with azafluorenocarbazole (2.84g, 10mmol) and performing the same synthesis as in 1b in example 1, 4.32g of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole was obtained as a white powder in 84% yield and 99.14% purity.
Figure BDA0001989877910000292
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), the same procedure as in example 1c in example 1 was repeated, thereby obtaining 2.73g of compound (139) as a white powder with a yield of 90% and a purity of 99.28%.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 603.7697, theoretical molecular weight: 603.7690, respectively; call for C44H33N3(％):C 87.53,H 5.51,N 6.96,Found:C 87.51,H 5.50,N 6.98。
Example 22: synthesis of Compound (144)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 21.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole
Figure BDA0001989877910000293
By substituting 2.83g, 10mmol of fluorenocarbazole in example 1 with 2.84g, 10mmol of the azafluorenocarbazole and 4-bromo-4 '-iodo-1, 1' -biphenyl (3.59g, 10mmol) with 4 '-bromo-3-iodo-1, 1' -biphenyl (3.59g, 10mmol), and following the same procedure as in 1b of example 1, 4.37g of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole was obtained as a white powder in 85% yield and 99.04% purity.
Synthesis of Compound (144)
Figure BDA0001989877910000301
The procedure of example 1 was otherwise the same as that of example 1c except for replacing 12- (4' -bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4' -bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole (2.58g, 5mmol) and diphenylamine (1.69g, 10mmol) with N-phenyl- [1,1' -biphenyl ] -4-amine (2.45g, 10mmol), whereby 2.95g of compound (144) was obtained as a white powder in 87% yield and 99.11% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 679.8676, theoretical molecular weight: 679.8670, respectively; call for C50H37N3(％):C 88.33,H 5.49,N 6.18,Found:C 88.34,H 5.50,N 6.15。
Example 23: synthesis of Compound (154)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 21.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole
Figure BDA0001989877910000302
By substituting 2.83g, 10mmol of fluorenocarbazole in example 1 with 2.84g, 10mmol of the azafluorenocarbazole and 3 '-bromo-3-iodo-1, 1' -biphenyl (3.59g, 10mmol) with 3 '-bromo-3-iodo-1, 1' -biphenyl (3.59g, 10mmol), and following the same procedure as in 1b of example 1, 4.36g of 12- (3 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole was obtained as a white powder in 85% yield and 99.08% purity.
Figure BDA0001989877910000303
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole (2.58g, 5mmol), diphenylamine (1.69g, 10mmol) with N-phenylnaphthalene-2-amine (2.19g, 10mmol), and by following the same procedure as in example 1c in example 1, 2.70g of compound (154) was obtained as a white powder in 83% yield and 99.18% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 653.8293, theoretical molecular weight: 653.8290, respectively; call for C48H35N3(％):C 88.18,H 5.40,N 6.43,Found:C 88.17,H 5.40,N 6.45。
Example 24: synthesis of Compound (160)
Synthesis of azafluorenocarbazoles:
the procedure was the same as for 1a in example 21.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole
The procedure was the same as for 1a in example 21.
Synthesis of Compound (160)
Figure BDA0001989877910000311
By substituting 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with the above-mentioned 12- (4 '-bromo- [1,1' -biphenyl ] -3-yl) -azafluorenocarbazole (2.58g, 5mmol), diphenylamine (1.69g, 10mmol) with 9, 9-dimethyl-N-phenyl-9H-fluoren-4-amine (2.85g, 10mmol), and by following the same procedure as in example 1c in example 1, 2.98g of the compound (160) was obtained as a white powder in 83% yield and 99.00% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 719.9327, theoretical molecular weight: 719.9320, respectively; call for C53H41N3(％):C 88.42,H 5.74,N 5.84,Found:C 88.40,H 5.75,N 5.85。
Example 25: synthesis of Compound (163)
Synthesis of azafluorenocarbazoles:
Figure BDA0001989877910000312
by substituting 2-chloroaniline (4.59g, 36mmol) in example 1 with 3-amino-2-chloropyridine (4.63g, 36mmol) and performing the same synthesis as in 1a in example 1, 8.68g of azafluorenocarbazole was obtained as a yellow powder in 85% yield and 99.07% purity.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
Figure BDA0001989877910000321
By substituting fluorenocarbazole (2.83g, 10mmol) in example 1 with azafluorenocarbazole (2.84g, 10mmol) and performing the same synthesis as in 1b in example 1, 4.36g of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole was obtained as a white powder in 85% yield and 99.02% purity.
Synthesis of Compound (163)
Figure BDA0001989877910000322
The procedure of example 1c was otherwise the same as that used in example 1 except for replacing 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 with 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), whereby 2.77g of compound (163) was obtained as a white powder in 92% yield and 99.20% purity.
Mass spectrometer MALDI-TOF-MS (m/z) ═ 603.7694, theoretical molecular weight: 603.7690, respectively; call for C44H33N3(％):C 87.53,H 5.51,N 6.96,Found:C 87.53,H 5.52,N 6.95。
Example 26: synthesis of Compound (191)
Synthesis of azafluorenocarbazoles:
the procedure was the same as in example 25 for 1a.
Synthesis of 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole
The procedure was the same as in example 25 for 1a.
Synthesis of Compound (191)
Figure BDA0001989877910000323
2.90g of compound (191) as a white powder was obtained in 84% yield and 99.09% purity in the same manner as in example 1 except that 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -fluorenocarbazole (2.57g, 5mmol) in example 1 was replaced with 12- (4 '-bromo- [1,1' -biphenyl ] -4-yl) -azafluorenocarbazole (2.58g, 5mmol), and diphenylamine (1.69g, 10mmol) was replaced with N-phenyldibenzofuran-4-amine (2.59g, 10 mmol).
Mass spectrometer MALDI-TOF-MS (m/z) ═ 693.8503, theoretical molecular weight: 693.8500, respectively; call for C50H35N3(％):C 86.55,H 5.08,N 6.06,Found:C 86.53,H 5.10,N 6.05。
Example 27: preparation of electronic components
The method comprises the following steps of sequentially ultrasonically cleaning an Indium Tin Oxide (ITO) glass substrate in a cleaning agent and deionized water for 1 h, then continuously ultrasonically cleaning the ITO glass substrate by acetone and isopropanol for 15min, carrying out vacuum drying for 2h (105 ℃), then carrying out UV ozone treatment for 15min, and conveying the ITO glass substrate to a vacuum evaporator.
4,4', 4-tris [ N- (naphthalene-2-yl) -N-phenyl-amino) ] triphenylamine (2T-NATA) was vacuum deposited on an ITO glass substrate to a thickness of 10nm to form a hole injection layer.
N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vacuum deposited on the hole injection layer to a thickness of 60nm to form a hole transport layer.
9, 10-bis (2-naphthyl) Anthracene (ADN) as a light-emitting layer host material and 4,4' -bis [4- (di-p-tolylamino) styryl ] biphenyl (DPAVBi) as a light-emitting layer guest material were co-vacuum deposited on the hole transport layer at a weight ratio of 94:6 to a thickness of 12nm to form a light-emitting layer.
3,3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 '-terphenyl ] -3, 3' -diyl ] bipyridine (TmPyPB) was vacuum deposited on the light-emitting layer to a thickness of 15nm to form an electron transport layer material.
Lithium fluoride (LiF) was vacuum-deposited on the electron transport layer to a thickness of 1nm to form an electron injection layer.
Magnesium (Mg) and aluminum (Al) mixed in a weight ratio of 90:10 were vacuum deposited on the electron injection layer to a thickness of 100nm to form a cathode.
The electronic component has a specific structure of ITO/2T-NATA (10nm)/NPB (60nm)/ADN 6 wt% DPAVBi (12nm)/TmPyPB (15nm)/LiF (1nm)/Mg Al (100nm)
The NPB was replaced with the compounds obtained in examples 1, 4,6, 8 to 13, 15 to 18, 21 to 22, and 24 to 25, and comparative compound 1, respectively, to complete the production of electronic devices.
Comparative product 1
Figure BDA0001989877910000331
The prepared electronic element is applied with forward bias direct current to detect the luminescence property, the thermal stability and the service life thereof, and the specific measurement method is as follows:
specific detection data are shown in table 1:
TABLE 1 characterization of electronic component Properties
Figure BDA0001989877910000341
As can be seen from table 1, the fluorenocarbazole derivative provided by the present invention, as a hole transport material, reduces the carrier injection energy barrier, thereby reducing the start voltage, and has the dual functions of hole transport and electron blocking, thereby improving the light emitting efficiency and light color of the device in the light emitting layer, having excellent thermal stability, and prolonging the lifetime of the device. Compared with NPB and a comparison product 1, the fluorenocarbazole derivative provided by the invention is a hole transport material with excellent comprehensive performance.
The compounds prepared in examples 1, 6, 8 to 10, 12 to 13, 15 to 18, 21 to 22 and 24 to 25 and comparative product 1 were used instead of ADN to complete the preparation of electronic devices.
The light emitting characteristics and the lifetime of the prepared electronic device were measured by applying a forward bias dc voltage to the electronic device, and the results are shown in table 2 below.
TABLE 2 electronic component Performance characterization
Figure BDA0001989877910000342
Figure BDA0001989877910000351
It can be seen from table 2 that the fluorenocarbazole derivative provided by the present invention has good injection characteristics for holes and electrons as a luminescent layer host material, and greatly limits the radiative luminescence of carriers in the luminescent layer, so that the device has excellent luminance and current efficiency, and the unique fluorenocarbazole derivative blue color generation enables the device to emit pure deep blue light, and compared with the prior art in which mCP and reference 1 are used as luminescent layer host materials, the fluorenocarbazole derivative has a higher glass transition temperature and a molecular orientation arrangement configuration, thereby solving the problems that the material is easy to decompose and be heated to crystallize in the evaporation process, and greatly improving the service life of the device. Compared with the prior art, the fluorenocarbazole derivative provided by the invention is a luminescent layer host material with excellent electroluminescent characteristics, thermal stability and service life.
In addition, as shown in FIG. 1, the ratio of ITO/2T-NATA (10nm)/NPB or the compound (99) of the present invention (60nm)/ADN: 6% DPAVBi or the compound (99) of the present invention: the energy level diagram of device 11 or device 18 prepared with a structure of 6% DPAVBi (12nm)/TmPyPB (15nm)/LiF (1nm)/Mg: 10% Al (100nm) is shown in FIG. 2 as the following, which is the case with ITO/2T-NATA (10nm)/NPB (60nm)/ADN: 6% DPAVBi or the compound of the present invention (99): 6% of DPAVBi (12nm)/TmPyPB (15nm)/LiF (1nm)/Mg: 10% of Al (100nm) is used as an energy level diagram of a device 18 or a device 27 prepared by the structure, so that compared with the conventional NPB or ADN, the fluorenocarbazole derivative provided by the invention has a wider energy gap, has the functions of hole transmission and electron blocking, and effectively limits excitons in a light-emitting layer, so that the fluorenocarbazole derivative becomes a more excellent hole transmission and light-emitting layer main body material.
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 (8)

1. A fluorenocarbazole derivative is characterized in that the general structural formula of the fluorenocarbazole derivative is shown as the following formula (I):
Figure FDA0002784425130000011
wherein X is CH or CR0Or N and one X is N, R0Selected from cyano, nitro, C1～20Alkyl of (C)1～20Alkoxy group of (C)1～20Alkylthio of, C6～45Aryloxy group of (A), C6～45Arylthio group of (a);
y is N or P ═ O;
R1、R2are each independently C6～45Aryl or C of3～45Heteroaryl of (A), R1And R2Same or different, said R1Or R2C of (A)6～45Is selected from: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthylphenyl, substituted or unsubstituted anthrylphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenylnaphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl; the R is1Or R2C of (A)3～45Is selected from: a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group;
n is 1,2 or 3.
2. The fluorenocarbazole derivative according to claim 1, characterized in that the fluorenocarbazole derivative comprises a compound of the following formula:
Figure FDA0002784425130000021
Figure FDA0002784425130000031
Figure FDA0002784425130000041
Figure FDA0002784425130000051
Figure FDA0002784425130000061
。
3. a method for producing a fluorenocarbazole derivative according to claim 1 or 2, characterized by comprising the steps of:
s1, carrying out SUZUKI reaction on 4-bromo-9, 9-dimethyl-9H-fluorene shown in formula (a) and X hetero 2-chloroaniline shown in formula (b) in the presence of a mixed system T1 of a metal catalyst, a ligand, alkali and a solvent to obtain X hetero N- (2-chlorophenyl) -9, 9-dimethyl-9H-fluorene-4-amine shown in formula (c);
s2: carrying out ring-closure reaction on X hetero N- (2-chlorphenyl) -9, 9-dimethyl-9H-fluorene-4-amine shown in the formula (c) in the presence of a mixed system T2 of a metal catalyst, a ligand, alkali and a solvent to obtain X hetero fluorenocarbazole shown in the formula (d);
s3: carrying out Ullmann reaction on X heterofluorenocarbazole shown in formula (d) and halogenated compound shown in formula (e) in the presence of a mixed system T3 of a metal catalyst, a ligand, alkali and a solvent to obtain a compound shown in formula (f);
s4: carrying out coupling reaction on a compound shown as a formula (f) and a compound shown as a formula (g) in the presence of a mixed system T4 of a metal catalyst, a ligand, alkali and a solvent to obtain a fluorenocarbazole derivative shown as a formula (I);
Figure FDA0002784425130000071
the catalysts in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 are respectively and independently selected from: at least one of tris (dibenzylideneacetone) dipalladium, palladium acetate, tetrakis (triphenylphosphine) palladium, cuprous iodide, [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium;
the ligands in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 are respectively and independently selected from: triphenylphosphine, tricyclohexylphosphine, 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, tri-tert-butylphosphine tetrafluoroborate and 18-crown-6;
the alkali existing in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 is respectively and independently selected from the following group: sodium tert-butoxide, cesium carbonate, potassium carbonate, sodium carbonate;
the solvents in the mixed system T1, the mixed system T2, the mixed system T3 and the mixed system T4 are respectively and independently selected from: at least one of toluene, xylene, N-methylpyrrolidone, ethanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, and water.
4. The preparation method of a fluorenocarbazole derivative according to claim 3, characterized in that the catalyst of the mixed system T1 is tris (dibenzylideneacetone) dipalladium, the ligand is triphenylphosphine or 2-dicyclohexyl-2, 4, 6-triisopropyl biphenyl, the base is potassium carbonate or sodium tert-butoxide, and the solvent is ethanol and water;
the catalyst of the mixed system T2 is palladium acetate, the ligand is tricyclohexylphosphine or tri-tert-butylphosphine tetrafluoroborate, the base is potassium carbonate or cesium carbonate, and the solvent is N, N-dimethylformamide or N-methylpyrrolidone;
the catalyst of the mixed system T3 is cuprous iodide, the ligand is 18-crown ether-6, the alkali is potassium carbonate, and the solvent is xylene or N, N-dimethylacetamide;
the catalyst of the mixed system T4 is tris (dibenzylideneacetone) dipalladium, the ligand is tri-tert-butylphosphine tetrafluoroborate, the base is sodium tert-butoxide, and the solvent is toluene.
5. A method for producing a fluorenocarbazole derivative according to claim 3,
in step S1, the materials are prepared according to the formula (a) shown in the specification, wherein the formula (a) is 4-bromo-9, 9-dimethyl-9H-fluorene, the formula (b) is Xhetero 2-chloroaniline, the formula (b) is shown in the specification, the formula (b) is a metal catalyst, the formula (b) is a ligand, and the formula (b) is a mixture of 1mmol of a solvent: 1.0-1.5 mmol: 0.005-0.02 mmol: 0.005-0.02 mmol: 2-4 mmol:2-10mL of the mixture is used for forming a mixed system T1;
in step S2, the materials were synthesized according to the general formula (c) for Xhetero N- (2-chlorophenyl) -9, 9-dimethyl-9H-fluoren-4-amine: metal catalyst: ligand: alkali: the solvent is 1 mmol: 0.02-0.2mmol, 0.01-0.3mmol, 2-5mmol, 2-10mL to form a mixed system T2;
in step S3, the materials are heterofluorenocarbazoles represented by formula (d): a halogenated compound represented by the formula (e): metal catalyst: ligand: alkali: the solvent is 1 mmol: 1-3 mmol: 0.1-0.5 mmol: 0.1-0.5 mmol:2-5mmol:2-10mL of the mixture is used for forming a mixed system T3;
in step S4, the materials are according to the formula (f): a compound represented by the formula (g): metal catalyst: ligand: alkali: the solvent is 1 mmol: 1-3 mmol: 0.005-0.02 mmol: 0.01-0.04 mmol: 2-4 mmol:2-10mL of the mixed system T4.
6. A method for producing a fluorenocarbazole derivative according to claim 3,
controlling the temperature of the mixed system T1 to be 60-80 ℃ during the SUZUKI reaction in the step S1;
the temperature of the mixed system T2 is controlled at 140-165 ℃ during the ring closure reaction in the step S2;
the temperature of the mixed system T2 is controlled at 140-165 ℃ when the Ullmann reaction is carried out in the step S3;
the temperature of the mixed system T2 is controlled to 90-115 ℃ when the coupling reaction is carried out in the step S4.
7. An electronic element comprising two electrodes and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer between the two electrodes, characterized in that the hole transport layer and/or the light emitting layer consist of the fluorenocarbazole derivative according to claim 1 or 2.
8. The electronic element according to claim 7, wherein the light-emitting layer is formed by doping a light-emitting host material with a light-emitting guest material, and wherein the light-emitting host material is composed of the fluorenocarbazole derivative.
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