CN109627255B

CN109627255B - Spiro donor organic light-emitting micromolecule material containing alkyl sulfur atom and preparation method and application thereof

Info

Publication number: CN109627255B
Application number: CN201910090109.1A
Authority: CN
Inventors: 苏仕健; 徐志达; 何燕梅; 李彬彬
Original assignee: South China University of Technology SCUT
Current assignee: South China University of Technology SCUT
Priority date: 2018-07-27
Filing date: 2019-01-29
Publication date: 2020-12-22
Anticipated expiration: 2039-01-29
Also published as: CN109627255A

Abstract

The invention discloses a spiro donor organic light-emitting micromolecule material containing alkyl sulfur atoms, wherein a spiro donor containing alkyl sulfur atoms and a triazine unit are used as skeleton units of acceptor composition molecules, and other aromatic amine compounds are connected to the spiro donor. The invention also discloses a preparation method and application of the organic light-emitting small molecular material. The luminescent material can realize intramolecular charge transfer effect, and the bipolar transmission characteristic thereof reduces the problem of unbalanced current carriers of the unipolar luminescent material, thereby simplifying the structure of the device and improving the performance of the device; due to the diversity of the external units and the high-efficiency characteristic of the external units, the luminescent material can be used as a high-efficiency blue luminescent material in an evaporation device and can also be used as a high-efficiency luminescent material in a non-doped solution processing device.

Description

Spiro donor organic light-emitting micromolecule material containing alkyl sulfur atom and preparation method and application thereof

Technical Field

The invention relates to the technical field of materials of an organic electroluminescent device technology, in particular to a spiro donor organic luminescent micromolecule material containing alkyl sulfur atoms and a preparation method and application thereof.

Background

Organic electroluminescent devices have been currently used in the field of light emitting displays. Compared with polymer luminescent materials, the small-molecule luminescent materials have the advantages of simple preparation process, definite molecular weight, single structure and the like, and therefore have more potential to be pushed to wider commercial application. At present, the technology for preparing the organic electroluminescent device with a multi-layer structure by using a small molecule material for vacuum evaporation or solution processing is continuously developing and advancing, and has made a great progress.

The conventional organic light emitting material generates 25% of singlet excitons and 75% of triplet excitons in the case of electro-excitation. However, whereas the process of transition of excitons of the singlet level to the ground state of a general fluorescent material is allowed, and the process of transition of excitons of the triplet level from the high energy state to the ground state is forbidden, the utilization rate of excitons thereof is always at a low level. Although the phosphorescent device can realize effective utilization of excitons by spin-orbit coupling of heavy metal atoms so that the internal quantum efficiency reaches 100%, the phosphorescent materials all contain precious rare metal elements (such as iridium and platinum) and are not favorable for reduction of production cost and strategic development direction of sustainable development. The thermal activation delayed fluorescence material can realize small energy difference between a singlet state energy level and a triplet state energy level through molecular design, so that triplet state excitons with slightly low energy and longer service life can be transited to the singlet state energy level through intersystem crossing in a certain temperature environment, and then delayed fluorescence is emitted. The development of the thermal excitation delayed fluorescence material plays a key role in improving the efficiency of the organic electroluminescent device, can avoid using noble metals of phosphorescent materials, and has positive significance for wider commercial application.

At present, the processes for preparing a device taking a thermal activation delayed fluorescence material as a luminescent layer mainly comprise vacuum evaporation and solution processing. The vacuum evaporation process is mature, but has the defects of complex process procedure and high cost, and the device prepared by solution processing has simple structure and low cost, and has important promotion significance for realizing large-area display of the OLED.

Therefore, to obtain a high-efficiency and stable organic electroluminescent device with practical value, not only the design of the device structure needs to be precisely controlled, but also very high requirements are made on the design of materials, especially luminescent materials, and the selection of the preparation process. Therefore, it is very important to explore the molecular structure design of the luminescent material and the corresponding performance relationship thereof, and provide guidance for preparing a luminescent molecule design idea which can show high efficiency, stability, low roll-off and long service life in a device.

Disclosure of Invention

In order to overcome the defects that the existing organic luminescent material containing a spiro structure is single in light color, basically has green light and is negative in preparation process, the invention aims to provide a spiro donor organic luminescent micromolecule material containing alkyl sulfur atoms, the external quantum efficiency and the luminescent color cover a wide range from blue light to sky blue light to green light, and the spiro donor organic luminescent micromolecule material can be applied to evaporation type devices.

The invention also aims to provide a preparation method of the spiro donor organic light-emitting small molecule material containing the alkyl sulfur atom.

The invention also aims at the application of the spiro donor organic light-emitting small molecule material containing the alkyl sulfur atom.

The purpose of the invention is realized by the following technical scheme:

the spiro donor organic light-emitting small molecule material containing the alkyl sulfur atom has any one chemical structure of P1n, P2n, P3n and P4 n:

wherein Ar is any atom or group of the following (1) to (5):

the spiro donor organic light-emitting small molecular material containing the alkyl sulfur atom has any one chemical structure of P1-P18:

the preparation method of the spiro donor organic light-emitting small molecular material containing the alkyl sulfur atom comprises the following steps: (1) preparing any one of intermediates having structures (a1) to (b 1):

(2) preparing any one of intermediates having structures (a2) to (b 2):

wherein Ar is any atom or group of the following (1) to (4):

(3) under the protection of inert gas, adding the intermediate prepared in the step (2), a triazine compound, alkali and a catalyst into an organic solvent, uniformly mixing, heating, refluxing, stirring and reacting, and carrying out cooling, extraction, spin-drying of the solvent and column chromatography to obtain the novel organic micromolecule luminescent material containing the spiro donor unit;

the molar ratio of the intermediate to the triazine compound is 1 (1-1.2).

Under the protection of nitrogen, dissolving the raw material monobromodianiline in anhydrous tetrahydrofuran, cooling to-70-80 ℃, sequentially adding N-butyl lithium solution and thioxanthone, recovering to room temperature, and then adding N₂Stirring overnight under the atmosphere, and adding ethanol to terminate the reaction after the reaction is finished; then spin-drying the solution, adding the reaction system into a mixed system of acetic acid and hydrochloric acid, heating to 80-90 ℃, and then extracting, drying, filtering and separating reactants to obtain a yellow solid;

the dosage of the n-butyl lithium is 1-1.5 times of the molar weight of the dibromophenylsulfide; the dosage of the thioxanthone is 1-1.5 times of the molar weight of the monobromodianiline.

Any one of intermediates with structures (a1) - (b1) prepared in the step (1) is specifically as follows:

under a nitrogen atmosphere, 1.0g of the yellow solid prepared in the previous step, 0.63g of N-iodosuccinimide and 80mL of dichloromethane are added in a 250mL three-neck flask. The reaction mixture was heated to 50 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. Removing dichloromethane by reduced pressure distillation, and purifying by silica gel column to obtain intermediate (b 1);

under a nitrogen atmosphere, 1.0g of the yellow solid prepared in the above step, 1.26g of N-iodosuccinimide and 80mL of dichloromethane are sequentially added into a 250mL three-neck flask. The mixture is heated to 60 ℃ and stirred for 48 hours in the dark. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. Methylene chloride was distilled off under reduced pressure, and the product was purified by silica gel column to obtain intermediate (a 1).

Any one of the intermediates having the structures (a2) to (b2) prepared in the step (2) is specifically:

dissolving the intermediate (a1) or (b1) in a dioxane solvent, sequentially adding an aromatic amine compound, alkali and a catalyst, uniformly mixing, heating, refluxing, stirring and reacting, and carrying out cooling, extraction, solvent spin-drying and column chromatography to obtain an intermediate unit;

the amount of the aromatic amine compound is 2-2.2 times of the molar amount of the intermediate (a1) or (b 1).

Heating, refluxing and stirring for reaction in the step (3), specifically:

the temperature is 90-110 ℃, and the reaction time is 12-24 h.

The triazine compound in the step (3) is any one of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-bromotriazine or 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-bromotriazine; the alkali is organic alkali, and the dosage of the alkali is 1.8-2.5 times of the molar equivalent of the aromatic amine compound; the catalyst consists of palladium acetate and tributyl phosphine; the organic solvent is toluene.

The spiro donor organic light-emitting small molecular material containing alkyl sulfur atoms is applied to an electroluminescent diode.

The organic luminous micromolecule material containing the spiro donor adopts the spiro donor containing alkyl sulfur atoms as a novel electron donor unit, and is connected with a common electron acceptor unit to obtain a molecule with a D-A structure, so that the organic luminous micromolecule material has the advantages of single structure, determined molecular weight, good repeatability of multiple synthesis and the like. The central benzene ring of the triazine acceptor unit and the spiro donor containing alkyl sulfur can form a larger dihedral angle, so that HOMO and LUMO of molecules can be effectively separated, and the energy level difference between a singlet state and a triplet state can be reduced. And because of the introduction of alkyl sulfur atoms, the conjugation of a donor diaryl structure is broken, and the electron donating property of a novel spiro donor unit can be effectively regulated and controlled, so that the luminescence blue shift of the luminescent material is realized, and the color purity of the material is improved. In addition, the organic light-emitting small molecular material can realize intramolecular charge transfer effect, has better bipolar transmission characteristic and is beneficial to the carrier balance in a light-emitting layer of a device. Meanwhile, compared with the known organic light-emitting small molecule material containing a spiro structure, the organic small molecule has higher horizontal orientation degree and higher fluorescence quantum yield, and can improve the light extraction efficiency of a device to obtain high external quantum efficiency and low efficiency roll-off. In addition, the solubility and the film forming property of the material are improved by introducing a high triplet state tert-butyl carbazole unit. Meanwhile, the grafted carbazole unit can effectively inhibit the interaction between luminescent molecules, weaken luminescence quenching caused by accumulation and endow the material with self-body property. Based on the characteristics, the organic micromolecule containing the spiro structure can also be used for preparing a high-efficiency non-doped solution processing device. Based on the above design principle, the spiro donor organic light-emitting micromolecule material containing alkyl sulfur atoms adjusts the position and the type of group connection, so that the light color of the material is adjusted, the intermolecular interaction force is reduced, the conjugation length, the electron cloud distribution, the carrier transmission characteristic, the solubility and the film forming property of the material are regulated, the device structure is finally simplified, the device performance is improved, the process cost is reduced, and the organic light-emitting micromolecule has a good industrial application prospect.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) compared with the existing organic luminescent material containing a spiral structure, the material provided by the invention has the characteristic of higher horizontal orientation degree, and can obtain higher external quantum efficiency; and due to the introduction of alkyl sulfur atoms, the electron donating property of the novel spiro donor unit can be regulated and controlled, so that the luminescent material has better luminescence and color purity.

(2) The spiro donor organic light-emitting micromolecule material containing the alkyl sulfur atom has the advantages of single structure, definite molecular weight, good solubility and film-forming property.

(3) The spiro donor organic light-emitting micromolecule material containing the alkyl sulfur atom can be applied to vacuum evaporation type devices, can also be applied to solution processing type devices, and has excellent performance, so the spiro donor organic light-emitting micromolecule material has very wide application prospect.

(4) The organic luminescent material containing the spiral structure can realize intramolecular charge transfer effect, and the bipolar transmission characteristic of the organic luminescent material reduces the problem of unbalanced current carriers of the unipolar luminescent material, thereby simplifying the structure of the device and improving the performance of the device.

(5) The carbonyl-containing spiro donor organic luminescent micromolecule material has a very wide application range in devices, and due to the diversity of external units and the characteristic of high efficiency of the external units, the carbonyl-containing spiro donor organic luminescent micromolecule material not only can be used as a high-efficiency blue light luminescent material in an evaporation device, but also can be used as a bipolar transmission main body in the devices, and can also be used as a high-efficiency luminescent material in a non-doping solution processing device with a simpler preparation process.

Drawings

FIG. 1 shows the emission spectra of P1 and P2 in toluene solution.

FIG. 2 shows absorption spectra of P1 and P2 in a toluene solution.

FIG. 3 is a spectrum of transient lifetime emission spectra of P1 and P2 in thin films.

Fig. 4 is a current density-voltage-luminance curve of an organic light emitting diode device comprising P1, P4, and a contrast molecule P19.

Fig. 5 is a luminance-external quantum efficiency curve of an organic light emitting diode device comprising P1, P4, and a comparative molecule P19.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

This example prepares intermediates 1 to 10 and compound P1:

the preparation method of the intermediate 1 (2-iodine 10H-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, 1.0g (2.8mmol) of spiro [ acridine-9, 9' -thioxanthene ], 0.63g (2.8mmol) of N-iodosuccinimide (NIS) and 80mL of Dichloromethane (DCM) were added in succession to a 250mL three-necked flask. The reaction mixture was heated to 50 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 0.95g of intermediate of formula 1, yield 90%, C25H16INS, M/Z489.37. m/z 489.00 (100.0%), 490.01 (27.0%), 491.00 (4.5%), 491.01 (2.7%), 492.00 (1.2%); elemental analysis: c, 61.36; h, 3.30; i, 25.93; n, 2.86; s, 6.55.

The preparation of the intermediate 2(2, 7-diiodo-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, 1.0g (2.8mmol) of spiro [ acridine-9, 9' -thioxanthene ], 1.26g (5.6mmol) of N-iodosuccinimide (NIS) and 80mL of Dichloromethane (DCM) were added in succession to a 250mL three-necked flask. The mixture is heated to 60 ℃ and stirred for 48 hours in the dark. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 0.95g of intermediate of formula 2, yield 90%, C25H16INS, M/Z615.27. m/z 489.00 (100.0%), 490.01 (27.0%), 491.00 (4.5%), 491.01 (2.7%), 492.00 (1.2%); elemental analysis: c, 61.36; h, 3.30; i, 25.93; n, 2.86; s, 6.55.

The preparation method of the intermediate 3(2- (carbazole-9-yl) -spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, 1.0g of intermediate 1(2.0mmol), 0.4g (2.1mmol) of carbazole, 1.38g (10mmol) of anhydrous potassium carbonate, 0.1g of cuprous iodide, 0.11g (1mmol) of trans-1, 2-cyclohexanediamine, and 80mL of dioxane were sequentially added to a 250mL three-necked flask. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 1.0g of intermediate of formula 3, yield 95%, C37H24N2S, M/Z528.67. m/z 528.17 (100.0%), 529.17 (40.0%), 530.17 (7.8%), 530.16 (4.5%), 531.17 (1.8%); elemental analysis: c, 84.06; h, 4.58; n, 5.30; and S, 6.06.

The preparation of the intermediate 4(2- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

1.0g of intermediate 1(2.0mmol), 0.6g (2.1mmol) of 3, 6-tert-butylcarbazole, 1.38g (10mmol) of anhydrous potassium carbonate, 0.1g of cuprous iodide, 0.11g (1mmol) of trans-1, 2-cyclohexanediamine and 80mL of dioxane were successively added to a 250mL three-necked flask under a nitrogen atmosphere. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 0.90g of intermediate of formula 4, yield 70%, C45H40N2S, M/Z640.89. m/z 640.29 (100.0%), 641.29 (48.7%), 642.30 (11.6%), 642.29 (4.5%), 643.29 (2.2%); elemental analysis: c, 84.34; h, 6.29; n, 4.37; s, 5.00.

The preparation method of the intermediate 5(2, 7-di (9H-carbazole-9-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, 1.2g of intermediate 2(2.0mmol), 0.8g (4.2mmol) of carbazole, 1.38g (10mmol) of anhydrous potassium carbonate, 0.1g of cuprous iodide, 0.11g (1mmol) of trans-1, 2-cyclohexanediamine, and 80mL of dioxane were successively added to a 250mL three-necked flask. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 1.1g of intermediate of formula 5, yield 80%, C49H31N3S, M/Z693.87. m/z 693.22 (100.0%), 694.23 (53.0%), 695.23 (13.8%), 695.22 (4.5%), 696.22 (2.4%), 696.23 (1.5%), 694.22 (1.1%); elemental analysis: c, 84.82; h, 4.50; n, 6.06; and S, 4.62.

The preparation of the intermediate 6(2, 7-bis (3, 6-di-tert-butyl-9H-carbazol-9-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

1.2g of intermediate 2(2.0mmol), 1.2g (4.2mmol) of 3, 6-tert-butylcarbazole, 1.38g (10mmol) of anhydrous potassium carbonate, 0.1g of cuprous iodide, 0.11g (1mmol) of trans-1, 2-cyclohexanediamine, and 80mL of dioxane were successively added to a 250mL three-necked flask under a nitrogen atmosphere. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 1.3g of intermediate of formula 6, yield 71%, C65H63N3S, M/Z918.30. m/z 917.47 (100.0%), 918.48 (70.3%), 919.48 (24.3%), 920.48 (4.7%), 919.47 (4.5%), 920.47 (3.2%), 918.47 (1.1%), 921.48 (1.1%); elemental analysis: c, 85.02; h, 6.92; n, 4.58; and S, 3.49.

The preparation of intermediate 7(2- (9'H- [9, 3': 6', 9' -carbazole ] -9 '-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, 1.0g of intermediate 1(2.0mmol), 9'H-9, 3': 6', 9 "-carbazole 0.4g (2.1mmol), anhydrous potassium carbonate 1.38g (10mmol), cuprous iodide 0.1g, trans-1, 2-cyclohexanediamine 0.11g (1mmol), dioxane 80 mL. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 1.5g of intermediate of formula 7, yield 87%, C61H38N4S, M/Z859.06. m/z 858.28 (100.0%), 859.29 (66.0%), 860.29 (21.4%), 860.28 (4.5%), 861.29 (3.7%), 861.28 (3.0%), 859.28 (1.5%); elemental analysis: c, 85.29; h, 4.46; n, 6.52; and S, 3.73.

The preparation of intermediate 8(2, 7-bis (9'H- [9, 3': 6', 9' -tert-carbazole ] -9 '-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, 1.2g of intermediate 2(2.0mmol), 9'H-9, 3': 6', 9 "-carbazole 0.8g (4.2mmol), anhydrous potassium carbonate 1.38g (10mmol), cuprous iodide 0.1g, trans-1, 2-cyclohexanediamine 0.11g (1mmol), dioxane 80 mL. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 2.2g of intermediate of formula 8, yield 88%, C97H59N7S, M/Z1354.65. m/z 1354.46 (100.0%), 1353.46 (95.3%), 1355.46 (40.8%), 1355.46 (11.2%), 1356.47 (11.1%), 1356.47 (6.0%), 1356.45 (4.5%), 1355.45 (4.3%), 1357.47 (4.1%), 1355.46 (2.6%), 1354.45 (2.5%), 1357.46 (1.8%), 1356.46 (1.1%); elemental analysis: c, 86.01; h, 4.39; n, 7.24; s, 2.37.

The preparation of intermediate 9(2- (3,3 ", 6, 6" -tetra-tert-butyl-9 'H- [9, 3': 6', 9' -tert-carbazol ] -9 '-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, a 250ml three-necked flask was charged with 1.0g of intermediate 1(2.0mmol), 3,3 ", 6, 6" -tetra-tert-butyl-9 'H-9, 3': 0.4g (2.1mmol) of 6', 9' -tertiary carbazole, 1.38g (10mmol) of anhydrous potassium carbonate, 0.1g of cuprous iodide, 0.11g (1mmol) of trans-1, 2-cyclohexanediamine, and 80mL of dioxane. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 1.8g of intermediate of structural formula 9 in 86% yield, C77H70N4S, M/Z1083.50. m/z 1082.53 (100.0%), 1083.54 (83.3%), 1084.54 (34.2%), 1085.54 (8.4%), 1084.53 (4.5%), 1085.53 (3.8%), 1086.55 (1.9%), 1086.53 (1.5%), 1083.53 (1.5%), 859.28 (1.5%); elemental analysis: c, 85.36; h, 6.51; n, 5.17; and S, 2.96.

The preparation of the intermediate 10(2, 7-bis (3,3 ", 6, 6" -tetra-tert-butyl-9 'H- [9, 3': 6', 9' -tert-carbazole ] -9 '-yl) -10H-thapiro [ acridine-9, 9' -thioxanthene ]) comprises the following steps:

under a nitrogen atmosphere, a 250ml three-necked flask was charged with 1.2g of intermediate 2(2.0mmol), 3,3 ", 6, 6" -tetra-tert-butyl-9 'H-9, 3': 0.8g (4.2mmol) of 6', 9' -tertiary carbazole, 1.38g (10mmol) of anhydrous potassium carbonate, 0.1g of cuprous iodide, 0.11g (1mmol) of trans-1, 2-cyclohexanediamine, and 80mL of dioxane. The reaction mixture was heated to 110 ℃ and stirred in the dark for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. Dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 3.0g of intermediate of formula 10, yield 83%, C129H123N7S, M/Z1803.51. m/z 1802.96 (100.0%), 1801.96 (71.7%), 1803.96 (69.2%), 1804.97 (15.2%), 1804.97 (8.4%), 1804.97 (8.2%), 1805.97 (6.0%), 1804.96 (4.5%), 1805.97 (3.7%), 1803.95 (3.2%), 1803.96 (2.6%), 1806.97 (2.2%), 1802.95 (1.9%), 1805.96 (1.7%), 1803.97 (1.4%), 1805.96 (1.4%), 1805.97 (1.2%), 1802.96 (1.0%); elemental analysis: c, 85.91; h, 6.87; n, 5.44; s, 1.78.

Compound P1(10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]) was prepared by the following steps:

the specific implementation steps are as follows:

in a 250ml three-necked flask, 1.0g (2.8mmol) of 10H, 10' H-spiro [ acridine-9, 9' -anthracene ] -10' one, 1.1g (2.8mmol) of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 0.90g of sodium tert-butoxide, 59.8mg of palladium acetate and tri-tert-butylphosphine were successively charged under a nitrogen atmosphere, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.50g of a product of the formula P1 in a yield of 81%. The molecular formula is as follows: C47H30N 4O; M/Z666.24 theory: M/Z666.24 (100.0%), 667.25 (50.8%), 668.25 (12.6%), 667.24 (1.5%), 669.25 (1.2%); elemental analysis C, 84.66; h, 4.54; n, 8.40; o, 2.40.

Example 2

This example prepares compound P2(10- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

1.0g (2.8mmol) of 10H-spiro [ acridine-9, 9' -thioxanthene ], 1.1g (2.8mmol) of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine and 0.90g of sodium tert-butoxide are added in succession to a 250ml three-necked flask under a nitrogen atmosphere, 59.8mg of palladium acetate and tri-tert-butylphosphine are added, and the mixture is heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.45g of a product of the formula P2 in a yield of 80%. The molecular formula is as follows: C46H30N 4S; M/Z670.83 theory: M/Z670.22 (100.0%), 671.22 (49.8%), 672.23 (12.1%), 672.21 (4.5%), 673.22 (2.2%), 673.23 (1.9%), 671.22 (1.5%); elemental analysis C, 82.36; h, 4.51; n, 8.35; s, 4.78.

Example 3

This example prepares compound P3(2- (9H-carbazol-9-yl) -10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine 9,9' -thiazole ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 1.0g (2.4mmol) of the intermediate 3, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and 59.8mg of palladium acetate and tritylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.20g of a product of the formula P3 in a yield of 76%. The molecular formula is as follows: C58H37N 5S; M/Z836.03 theoretical value M/Z835.28 (100.0%), 836.28 (62.7%), 837.28 (19.3%), 837.27 (4.5%), 838.29 (3.1%), 838.28 (2.8%), 836.27 (1.8%), 837.28 (1.2%); elemental analysis C, 83.33; h, 4.46; n, 8.38; and S, 3.83.

Example 4

This example prepares compound P4(2- (9H-carbazol-9-yl) -10- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine 9,9' -thioxanthene ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 1.0g (2.4mmol) of the intermediate 3, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and 59.8mg of palladium acetate and tritylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.20g of a product of the formula P4 in a yield of 76%. The molecular formula is as follows: C58H37N 5S; M/Z836.03 theoretical value M/Z835.28 (100.0%), 836.28 (62.7%), 837.28 (19.3%), 837.27 (4.5%), 838.29 (3.1%), 838.28 (2.8%), 836.27 (1.8%), 837.28 (1.2%); elemental analysis C, 83.33; h, 4.46; n, 8.38; and S, 3.83.

Example 5

This example prepares compound P5(2, 7-bis (9H-carbazol-9-yl) -10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ aza-9, -9,9' -thioxanthene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

1.4g (2.3mmol) of the intermediate 5, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and then 59.8mg of palladium acetate and tri-tert-butylphosphine were added in a 250ml three-necked flask under a nitrogen atmosphere, heated to 110 ℃ and stirred with the exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.70g of a product of the formula P5 in a yield of 80%. The molecular formula is as follows: C70H44N 6S; M/Z is 1001.22 theoretical value M/Z1000.33 (100.0%), 1001.34 (75.7%), 1002.34 (28.3%), 1003.34 (6.1%), 1002.33 (4.5%), 1003.33 (3.4%), 1001.33 (2.2%), 1002.34 (1.7%), 1004.34 (1.3%); elemental analysis C, 83.97; h, 4.43; n, 8.39; and S, 3.20.

Example 6

This example prepares compound P6(2, 7-bis (9H-carbazol-9-yl) -10- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ aza-9, -9,9' -thioxanthene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

1.4g (2.3mmol) of the intermediate 5, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and then 59.8mg of palladium acetate and tri-tert-butylphosphine were added in a 250ml three-necked flask under a nitrogen atmosphere, heated to 110 ℃ and stirred with the exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.70g of a product of the formula P6 in a yield of 80%. The molecular formula is as follows: C70H44N 6S; M/Z is 1001.22 theoretical value M/Z1000.33 (100.0%), 1001.34 (75.7%), 1002.34 (28.3%), 1003.34 (6.1%), 1002.33 (4.5%), 1003.33 (3.4%), 1001.33 (2.2%), 1002.34 (1.7%), 1004.34 (1.3%); elemental analysis C, 83.97; h, 4.43; n, 8.39; and S, 3.20.

Example 7

This example prepares compound P7(2- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

1.4g (2.3mmol) of the intermediate 4, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and then 59.8mg of palladium acetate and tri-tert-butylphosphine were added in a 250ml three-necked flask under a nitrogen atmosphere, heated to 110 ℃ and stirred with the exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. Dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 1.53g of a product of the formula P7 in a yield of 72%. Molecular formula C66H53N 5S; M/Z is 948.25 theory M/Z947.40 (100.0%), 948.41 (71.4%), 949.41 (25.1%), 950.41 (5.0%), 949.40 (4.5%), 950.40 (3.2%), 948.40 (1.8%), 949.40 (1.3%), 951.40 (1.1%); elemental analysis C, 83.60; h, 5.63; n, 7.39; and S, 3.38.

Example 8

This example prepares compound P8(2- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -10- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

1.4g (2.3mmol) of the intermediate 4, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and then 59.8mg of palladium acetate and tri-tert-butylphosphine were added in a 250ml three-necked flask under a nitrogen atmosphere, heated to 110 ℃ and stirred with the exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. Dichloromethane was distilled off under reduced pressure and purified by silica gel column to obtain 1.53g of a product of the formula P8 in a yield of 72%. Molecular formula C66H53N 5S; M/Z is 948.25 theory M/Z947.40 (100.0%), 948.41 (71.4%), 949.41 (25.1%), 950.41 (5.0%), 949.40 (4.5%), 950.40 (3.2%), 948.40 (1.8%), 949.40 (1.3%), 951.40 (1.1%); elemental analysis C, 83.60; h, 5.63; n, 7.39; and S, 3.38.

Example 9

This example prepares compound P9(2, 7-bis (3, 6-di-tert-butyl-9H-carbazol-9-yl) -10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 1.9g (2.3mmol) of intermediate 6, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and 59.8mg of palladium acetate and tritylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 2.15g of a product of the formula P9 in a yield of 80%. Molecular formula C86H76N 6S; M/Z is 1225.66 theory M/Z1224.59 (100.0%), 1225.59 (93.0%), 1226.59 (42.8%), 1227.60 (11.7%), 1226.58 (4.5%), 1227.58 (4.2%), 1228.60 (2.9%), 1225.58 (2.2%), 1226.59 (2.1%), 1228.59 (1.9%), 1227.60 (1.3%); elemental analysis C, 84.28; h, 6.25; n, 6.86; s, 2.62.

Example 10

This example prepares compound P10(2, 7-bis (3, 6-di-tert-butyl-9H-carbazol-9-yl) -10- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 1.9g (2.3mmol) of intermediate 6, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and 59.8mg of palladium acetate and tritylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 2.15g of a product of the formula P10 in a yield of 80%. Molecular formula C86H76N 6S; M/Z is 1225.66 theory M/Z1224.59 (100.0%), 1225.59 (93.0%), 1226.59 (42.8%), 1227.60 (11.7%), 1226.58 (4.5%), 1227.58 (4.2%), 1228.60 (2.9%), 1225.58 (2.2%), 1226.59 (2.1%), 1228.59 (1.9%), 1227.60 (1.3%); elemental analysis C, 84.28; h, 6.25; n, 6.86; s, 2.62.

Example 11

This example prepares compound P11(2- (9' H- [9,3 ': 6', 9 "-carbazole ] -9' -yl) -10- (4- (4, 6-diphenyl-1, 3, 5-triazine) -pyridin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

1.4g (2.3mmol) of the intermediate 7, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and then 59.8mg of palladium acetate and tri-tert-butylphosphine were added in succession to a 250ml three-necked flask under a nitrogen atmosphere, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.80g of a product of the formula P11 in a yield of 78%. Molecular formula C82H51N 7S; M/Z is 1166.42 theoretical value M/Z1165.39 (100.0%), 1166.40 (88.7%), 1167.40 (38.8%), 1168.40 (10.4%), 1167.39 (4.5%), 1168.39 (4.0%), 1166.39 (2.6%), 1167.39 (2.3%), 1169.41 (2.0%), 1169.40 (1.8%), 1168.40 (1.0%); elemental analysis C, 84.44; h, 4.41; n, 8.41; s, 2.75.

Example 12

This example prepares compound P12(2- (9' H- [9,3 ': 6', 9 "-carbazole ] -9' -yl) -10- (3- (4, 6-diphenyl-1, 3, 5-triazine) -pyridin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), whose structural formula and synthetic route are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 1.4g (2.3mmol) of intermediate 20, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and 59.8mg of palladium acetate and tritylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.80g of a product of the formula P12 in a yield of 78%. Molecular formula C82H51N 7S; M/Z is 1166.42 theoretical value M/Z1165.39 (100.0%), 1166.40 (88.7%), 1167.40 (38.8%), 1168.40 (10.4%), 1167.39 (4.5%), 1168.39 (4.0%), 1166.39 (2.6%), 1167.39 (2.3%), 1169.41 (2.0%), 1169.40 (1.8%), 1168.40 (1.0%); elemental analysis C, 84.44; h, 4.41; n, 8.41; s, 2.75.

Example 13

This example prepares compound P13(2, 7-bis (9'H- [9, 3': 6', 9' -tert-carbazol ] -9 '-yl) -10- (4- (4, 6-diphenyl-1, 3,5) -triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), the structural formula and the synthetic route of which are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, a 250ml three-necked flask was charged with 2.2g (2.3mmol) of intermediate 8, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, 59.8mg of palladium acetate and tritylphosphine were added, heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 2.7g of a product of the formula P13 in a yield of 76%. Molecular formula C118H72N 10S; M/Z is 1662.00 theoretical value M/Z1661.57 (100.0%), 1660.57 (78.4%), 1662.57 (33.5%), 1662.57 (29.8%), 1663.58 (21.7%), 1664.58 (5.4%), 1663.58 (4.7%), 1663.57 (4.5%), 1662.57 (3.7%), 1662.56 (3.5%), 1661.56 (2.9%), 1664.58 (2.3%), 1665.58 (1.7%), 1664.57 (1.5%), 1664.57 (1.3%), 1663.57 (1.2%), 1663.57 (1.1%); elemental analysis C, 85.28; h, 4.37; n, 8.43; s, 1.93.

Example 14

This example prepares compound P14(2, 7-bis (9'H- [9, 3': 6', 9' -tert-carbazol ] -9 '-yl) -10- (3- (4, 6-diphenyl-1, 3,5) -triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), the structural formula and the synthetic route of which are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 2.2g (2.3mmol) of intermediate 8, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, 59.8mg of palladium acetate and trite-butylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 2.7g of a product of the formula P14 in a yield of 76%. Molecular formula C118H72N 10S; M/Z is 1662.00 theoretical value M/Z1661.57 (100.0%), 1660.57 (78.4%), 1662.57 (33.5%), 1662.57 (29.8%), 1663.58 (21.7%), 1664.58 (5.4%), 1663.58 (4.7%), 1663.57 (4.5%), 1662.57 (3.7%), 1662.56 (3.5%), 1661.56 (2.9%), 1664.58 (2.3%), 1665.58 (1.7%), 1664.57 (1.5%), 1664.57 (1.3%), 1663.57 (1.2%), 1663.57 (1.1%); elemental analysis C, 85.28; h, 4.37; n, 8.43; s, 1.93.

Example 15

This example prepares compound P15(10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -2- (3, 3', 6, 6' -tetra-tert-butyl-9 'H- [9, 3': 6', 9' -carbazol ] -9 '-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 1.8g (2.3mmol) of intermediate 9, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and 59.8mg of palladium acetate and tritylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified with a silica gel column to obtain 2.33g of a product of the formula P15 in 84% yield. Molecular formula C98H83N 7S; M/Z is 1390.85 theoretical value M/Z1390.65 (100.0%), 1389.64 (94.3%), 1391.65 (40.3%), 1391.65 (12.1%), 1392.65 (11.0%), 1392.65 (6.4%), 1392.64 (4.5%), 1391.64 (4.3%), 1393.66 (4.2%), 1391.64 (2.6%), 1390.64 (2.4%), 1393.65 (2.4%), 1392.65 (1.0%); elemental analysis C, 84.63; h, 6.02; n, 7.05; s, 2.31.

Example 16

This example prepares compound P16(10- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -2- (3, 3', 6, 6' -tetra-tert-butyl-9 'H- [9, 3': 6', 9' -carbazol ] -9 '-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 1.8g (2.3mmol) of intermediate 9, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, and 59.8mg of palladium acetate and tritylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified with a silica gel column to obtain 2.33g of a product of the formula P16 in 84% yield. Molecular formula C98H83N 7S; M/Z is 1390.85 theoretical value M/Z1390.65 (100.0%), 1389.64 (94.3%), 1391.65 (40.3%), 1391.65 (12.1%), 1392.65 (11.0%), 1392.65 (6.4%), 1392.64 (4.5%), 1391.64 (4.3%), 1393.66 (4.2%), 1391.64 (2.6%), 1390.64 (2.4%), 1393.65 (2.4%), 1392.65 (1.0%); elemental analysis C, 84.63; h, 6.02; n, 7.05; s, 2.31.

Example 17

This example prepares compound P17(10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -2, 7-bis (3, 3', 6, 6' -tetra-tert-butyl-9 'H- [9, 3': 6', 9' -carbazol ] -9 '-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 4.1g (2.3mmol) of intermediate 10, 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, 59.8mg of palladium acetate and trite-butylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 3.31g of a product of the formula P17 in a yield of 70%. Molecular formula C150H136N 10S; M/Z is a theoretical value of 2109.07, M/Z is 2110.07 (100.0%), 2109.07 (61.6%), 2111.07 (54.2%), 2111.07 (26.4%), 2112.08 (26.2%), 2112.08 (16.8%), 2113.08 (13.5%), 2114.08 (4.8%), 2112.07 (4.5%), 2113.08 (3.6%), 2111.06 (2.8%), 2111.07 (2.6%), 2113.07 (2.5%), 2112.07 (2.4%), 2110.06 (1.6%), 2111.08 (1.6%), 2115.09 (1.3%), 2113.07 (1.2%), 2113.07 (1.2%), 2114.07 (1.2%), 2111.07 (1.1%); elemental analysis C, 85.35; h, 6.49; n, 6.64; s, 1.52.

Example 18

This example prepares compound P18(10- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -2, 7-bis (3, 3', 6, 6' -tetra-tert-butyl-9 'H- [9, 3': 6', 9' -carbazol ] -9 '-yl) -10H-spiro [ acridine-9, 9' -thioxanthene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

under a nitrogen atmosphere, 4.1g (2.3mmol) of intermediate 10, 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine 1.1g (2.8mmol),0.90g of sodium tert-butoxide, 59.8mg of palladium acetate and trite-butylphosphine were added successively in a 250ml three-necked flask, and the mixture was heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 3.31g of a product of the formula P18 in a yield of 70%. Molecular formula C150H136N 10S; M/Z is a theoretical value of 2109.07, M/Z is 2110.07 (100.0%), 2109.07 (61.6%), 2111.07 (54.2%), 2111.07 (26.4%), 2112.08 (26.2%), 2112.08 (16.8%), 2113.08 (13.5%), 2114.08 (4.8%), 2112.07 (4.5%), 2113.08 (3.6%), 2111.06 (2.8%), 2111.07 (2.6%), 2113.07 (2.5%), 2112.07 (2.4%), 2110.06 (1.6%), 2111.08 (1.6%), 2115.09 (1.3%), 2113.07 (1.2%), 2113.07 (1.2%), 2114.07 (1.2%), 2111.07 (1.1%); elemental analysis C, 85.35; h, 6.49; n, 6.64; s, 1.52.

Example 19

This example prepared a comparative compound P19(10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -10H-spiro [ acridine-9, 9' -fluorene ]), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

1.0g (2.8mmol) of 10H-spiro [ acridine-9, 9' -fluorene ] and 1.1g (2.8mmol) of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine are successively charged into a 250ml three-necked flask under a nitrogen atmosphere, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tritylphosphine are further charged, and the mixture is heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. Dichloromethane was distilled off under reduced pressure and purified by a silica gel column to obtain 1.45g of a product of the formula P19 in 83% yield. The molecular formula is as follows: C46H30N 4; M/Z638.77 theory: M/Z638.25 (100.0%), 639.25 (49.8%), 640.25 (12.1%), 641.26 (1.9%), 639.24 (1.5%); elemental analysis C, 86.49; h, 4.73; n, 8.77.

The following are examples of the use of the compounds of the present invention in Organic Light Emitting Diode (OLED) devices:

examples 20 to 25

The compound of the invention is used as a luminescent material of an OLED device, and the structure of the implemented universal device is as follows:

ITO(95nm)/TAPC(20nm)/mCP(10nm)/Pn(20wt％):DPEPO(30nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)

wherein ITO is an anode, TAPC is a hole injection layer, CBP is a luminescent material doped main body TmPyPB is an electron transport layer, LiF is an electron injection layer, and Al is a cathode.

The structural formula of the used material is as follows:

the device preparation process is as follows: carrying out ultrasonic treatment on the ITO transparent conductive glass in a cleaning agent, and then cleaning the ITO transparent conductive glass by deionized water, wherein the ultrasonic treatment is carried out in the presence of acetone: ultrasonic degreasing in mixed solvent of ethanol, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding with low-energy cations.

The glass with the anode ITO is placed in a vacuum chamber and is vacuumized to 1 multiplied by 10^-5～9×10^-3Pa on the anode film

The deposition rate of (2) evaporating and plating the organic material layer, wherein in evaporating and plating the luminous layer, the CBP and the luminous material are respectively placed on two evaporation plating sources, and the mixing proportion of the CBP and the luminous material is controlled by a certain deposition rate. Then is followed by

Evaporating LiF at a deposition rate of

The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.

The current density-voltage-luminance graph and the external quantum efficiency-luminance graph of the organic light emitting diode device of the present example are shown in fig. 4 and 5, and the basic characterization data are shown in table 1.

Transient lifetime spectra of P1 and P2 in the thin film of this example are shown in fig. 3, and the lifetime decay has obvious secondary decay characteristics, a large number of long-life components and a lifetime length reaching microsecond scale, which proves that the molecules are molecules with heat-activated delayed fluorescence characteristics.

Table 1 test results of the OLED device prepared

Description of the drawings: the organic light-emitting micromolecules containing the spiro structures take triphenyltriazine with large plane structures and high triplet state energy levels as an acceptor, and take spiro units containing alkyl sulfur atoms as donor units, so that excellent device performance and light color are shown.

By comparing the data in the table, it can be found that the organic light-emitting small molecule containing the spiro structure can obtain the current efficiency of 75.6cd/A and the external quantum efficiency of 32.2% in a simple device structure when being applied to an evaporation device. Meanwhile, the electroluminescent color of the device prepared based on the molecules is between blue light and sky blue light, so that the blue light color can be kept, and the electroluminescent color purity of the device can be kept. The design of the high-efficiency blue light material is always the key point and the difficulty of research in the field of organic electroluminescent materials, and the organic luminescent micromolecules containing the spiro structures not only realize better blue light emission, but also achieve quite excellent levels of current efficiency and external quantum efficiency. The current efficiency, external quantum efficiency and color purity of the device of the luminescent molecule of the invention are obviously superior to those of the device of the comparative example molecule P19 in the same device structure, thus providing a novel and advanced design idea of the high-efficiency blue light material.

Examples 26 to 30

Example 30

This example prepared the comparative compound P20(10- (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -9, 9-dimethyl-9, 10-dihydroacridine), the structural formula and synthetic route of which are shown below:

the specific implementation steps are as follows:

in a 250ml three-necked flask under a nitrogen atmosphere, 1.1g (2.8mmol) of 9, 9-dimethyl-9, 10-dihydroacridine, 1.1g (2.8mmol) of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine and 0.90g of sodium tert-butoxide are successively added, and 59.8mg of palladium acetate and tri-tert-butylphosphine are further added, and the mixture is heated to 110 ℃ and stirred with exclusion of light for 24 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The methylene chloride was distilled off under reduced pressure and purified by a silica gel column to obtain 1.30g of a product of the formula P20 in a yield of 90%. The molecular formula is as follows: C36H28N 4; M/Z516.65 theoretical M/Z516.23 (100.0%), 517.23 (38.9%), 518.24 (7.4%), 517.23 (1.5%); elemental analysis C, 83.69; h, 5.46; n, 10.84.

The compound of the invention is used as a luminescent material for processing a non-doped OLED device by solution, and the implemented general device has the following structure:

ITO (95nm)/(PEDOT: PSS) (30nm)/Pn (30nm)/TmPyPB (50nm)/LiF (1nm)/Al (100nm), wherein PEDOT: PSS is a hole injection layer, TmPyPB is an electron transport layer, LiF is an electron injection layer, and Al is a cathode.

The device preparation process is as follows:

the PEDOT PSS layer was coated on a previously cleaned ITO glass plate by a spin coating method, followed by drying at 150 ℃ for ten minutes. Then spin-coating luminescent layer material, dissolving the material in chlorobenzene with the concentration of 8.6mg mL^-1And then dried at 100 ℃ for 10 minutes. And then evaporating the electron transport layer and the cathode material, wherein the method and the parameters are consistent with those of an evaporation device.

The results of the maximum external quantum efficiency, the maximum current efficiency, the lighting voltage and the light color characterization data of the organic light emitting diode device of the present embodiment are shown in table 2.

Table 2 test results of pure film solution processed OLED devices prepared in table 2

Description of the drawings: the organic light-emitting micromolecules containing the spiro structures take triphenyltriazine with large plane structures and high triplet state energy levels as an acceptor, and take the spiro units containing alkyl sulfur atoms and grafted aromatic compounds as donor units, so that excellent device performance and light color are shown.

The tertiary butyl carbazole is grafted at the periphery of the donor unit, so that the distribution of HOMO is concentrated in the peripheral carbazole unit, the HOMO and LUMO are well separated, and the material is endowed with good solubility and film-forming property, so that the molecules of the structure containing the tertiary butyl carbazole are very suitable for being used as a luminescent material for processing an OLED device by using solution, the preparation process is greatly simplified, and the process cost is reduced. More importantly, the tert-butyl carbazole enables molecules to have self-host properties, aggregation quenching of the molecules can be effectively inhibited without using other host materials in the device, and the single material is used as the light emitting layer of the device, so that the preparation process of the device can be further simplified.

Compared with P20 similar structure molecules with excellent performance in undoped solution processing devices, due to the high-level orientation and grafting carbazole of the molecules, the undoped solution processing device based on P9 and P17 has the advantages that the starting voltage is 3.8V, the maximum current efficiency is as high as 56.3cd/A, the maximum external quantum efficiency is as high as 22.5%, and more excellent performance is shown.

Generally speaking, the series of spiro-structure organic small molecule materials containing alkyl sulfur atoms have a very wide application range in OLED devices, and due to the diversity of external units and the characteristic of high efficiency of the external units, the spiro-structure organic small molecule materials not only can be used as high-efficiency blue light emitting materials in evaporation devices, but also can be used as high-efficiency light emitting materials in non-doped solution processing devices with simpler preparation processes. This wide range of applications is also a feature and advantage of this family of materials.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims

1. The spiro donor organic light-emitting small molecule material containing the alkyl sulfur atom is characterized by having any one chemical structure of P1n, P2n, P3n and P4 n:

wherein Ar is any atom or group of the following (1) to (5):

2. the spiro donor organic light-emitting small molecule material containing an alkyl sulfur atom according to claim 1, having any one of the chemical structures P1-P18:

3. the preparation method of the spiro donor organic light-emitting micromolecule material containing the alkyl sulfur atom is characterized by comprising the following steps of:

(1) preparing any one of intermediates having structures (a1) to (b 1):

(2) preparing any one of intermediates having structures (a2) to (b 2):

wherein Ar is any atom or group of the following (1) to (4):

(3) under the protection of inert gas, adding the intermediate prepared in the step (2), a triazine compound, alkali and a catalyst into an organic solvent, uniformly mixing, heating, refluxing, stirring, reacting, cooling, extracting, spin-drying the solvent, and performing column chromatography to obtain the organic micromolecule luminescent material based on the spiro donor unit containing alkyl sulfur;

the molar ratio of the intermediate to the triazine compound is 1 (1-1.2); the triazine compound is any one of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-bromotriazine or 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-bromotriazine; the alkali is organic alkali, and the dosage of the alkali is 1.8-2.5 times of the molar equivalent of the aromatic amine compound.

4. The method for preparing spiro donor organic light-emitting small molecule material containing alkyl sulfur atom according to claim 3, wherein step (1) is to prepare any one of intermediates having structures (a1) to (b1), specifically:

under the nitrogen atmosphere, 1.0g of spiro [ acridine-9, 9' -thioxanthene ], 0.63g of N-iodosuccinimide and 80mL of dichloromethane are added into a 250mL three-neck flask in sequence; heating to 50 ℃, and stirring in the dark for reaction for 24 hours; after the reaction is finished, suspending the solvent in the reaction system, extracting for three times by using dichloromethane and water, and taking an organic phase; removing dichloromethane by reduced pressure distillation, and purifying by silica gel column to obtain intermediate (b 1);

under the nitrogen atmosphere, 1.0g of spiro [ acridine-9, 9' -thioxanthene ], 1.26g of N-iodosuccinimide and 80mL of dichloromethane are added into a 250mL three-neck flask in sequence; heating to 60 ℃, and stirring in the dark for reaction for 48 hours; after the reaction is finished, suspending the solvent in the reaction system, extracting for three times by using dichloromethane and water, and taking an organic phase; methylene chloride was distilled off under reduced pressure, and the product was purified by silica gel column to obtain intermediate (a 1).

5. The method for preparing spiro donor organic light-emitting small molecule material containing alkyl sulfur atom according to claim 4, wherein any one of the intermediates having the structures of (a2) to (b2) prepared in step (2) is specifically:

6. The method for preparing the spiro donor organic light-emitting small molecule material containing the alkyl sulfur atom according to claim 3, wherein the heating reflux stirring reaction in the step (3) is specifically as follows:

the temperature is 90-110 ℃, and the reaction time is 12-24 h.

7. The method for preparing the spiro donor organic light-emitting small molecule material containing alkyl sulfur atom according to claim 3, wherein the catalyst is composed of palladium acetate and tributyl phosphine; the organic solvent is toluene.

8. Use of the spiro donor organic light-emitting small molecule material containing alkyl sulfur atoms as claimed in any one of claims 1 to 2 in an electroluminescent diode.