CN109503427B

CN109503427B - D-A type organic blue fluorescent material and preparation method and application thereof

Info

Publication number: CN109503427B
Application number: CN201811619632.0A
Authority: CN
Inventors: 胡鉴勇; 张佳丽; 赵振; 段雪伟
Original assignee: Shaanxi Normal University
Current assignee: Shaanxi Normal University
Priority date: 2018-12-28
Filing date: 2018-12-28
Publication date: 2021-10-08
Anticipated expiration: 2038-12-28
Also published as: CN109503427A

Abstract

The invention relates to a D-A type organic blue fluorescent material and a preparation method and application thereof, wherein a molecular design strategy of the material is to take benzene as a central pi conjugated bridge chain, and two anthracene light-emitting units (a group with an electron supply characteristic and a group with an electron absorption characteristic) are respectively connected at the meta position of the benzene to regulate and control the pi conjugated form and the intramolecular charge transfer path of material molecules, so that the deep blue emission of the material molecules is realized, and the injection balance of carriers in the application of an OLED device is realized. On the other hand, a group with electron donating property or an electron withdrawing property is introduced to the central benzene pi conjugated bridge chain to further inhibit the pi-pi stacking effect among material molecules, so that high luminescent quantum efficiency of the material molecules is realized, and the D-A type organic blue fluorescent material is prepared and has good thermal stability and high luminescent quantum efficiency.

Description

D-A type organic blue fluorescent material and preparation method and application thereof

[ technical field ] A method for producing a semiconductor device

The invention relates to the field of organic electroluminescent diodes, in particular to a D-A type organic blue fluorescent material and a preparation method and application thereof.

[ background of the invention ]

Compared with the conventional Liquid Crystal Display (LCD), Organic Light-Emitting Diodes (OLEDs) are considered as the most competitive technologies in the fields of new generation display and all-solid-state lighting because of their characteristics of all-solid-state, self-luminescence, wide viewing angle, low-voltage driving, flexibility, etc. Through thirty years of effort, the OLED has made great progress in brightness, efficiency, lifetime, etc., and has been given a new commercial prospect. Nevertheless, the OLED still has the problems of short lifetime and low efficiency of blue light emitting materials and devices, and is yet to be further explored by researchers.

To realize a full color display, three primary colors (red, green, blue) are indispensable. The red and green materials used in the OLED are relatively mature and can substantially meet the requirements of commercialization, but the number of blue materials, especially the number of efficient and stable deep blue luminescent materials is relatively small, which greatly affects the industrialization process of the OLED. For a good blue light material, not only good color purity but also good thermal stability, high luminous efficiency, easy sublimation and the like are required, so that a good blue light material, especially a deep blue light material, is difficult to obtain. Although many anthracene derivatives have been developed so far, and are successfully applied to OLED devices as host or guest light-emitting materials, most of these materials have the characteristics of difficult synthesis, difficult purification, easy crystallization, poor stability, and the like, resulting in low efficiency and short lifetime of OLED devices. Therefore, further development of efficient and stable organic blue light emitting materials has more realistic significance to promote the commercialization process of the OLED.

[ summary of the invention ]

The invention aims to overcome the defects of the prior art and provides a D-A type organic blue fluorescent material and a preparation method and application thereof; the prepared material has good thermal stability and high luminous quantum efficiency, and is applied to non-doped deep blue OLED devices, and the material has excellent performance and high External Quantum Efficiency (EQE).

In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:

a D-A type organic blue fluorescent material has the following structural formula:

wherein: r₁Refers to a group of electron donating character, R₂Radicals indicating electron-withdrawing character, R₃、R₄Refers to neutral groups, groups of electron donating character or groups of electron withdrawing character.

The invention is further improved in that:

preferably, wherein R is₁Is CH₃、OCH₃、C₂H₅、OC₂H₅Or C (CH)₃)₃；R₂Is F, CF₃CN or CHO; r₃、R₄Is H, CH₃、OCH₃、C₂H₅、OC₂H₅、C(CH₃)₃、F、CF₃CN or CHO.

A D-A type organic blue fluorescent material is prepared by Suzuki coupled reaction of a substance B and 9-bromo-10- (4-electron-withdrawing substitution) phenylanthracene, wherein the substance B is 3- [10- (4-electron-donating substitution) phenylanthracene]-4,5, 6-trisubstituted phenylboronate; wherein the electron-withdrawing substitution in the 9-bromo-10- (4-electron-withdrawing substitution) phenylanthracene is F, CF₃Any one of CN or CHO; 3- [10- (4-Electron donating substituted) benzanthracene]-4,5, 6-trisubstituted phenylboronic acid ester with an electron substitution of CH₃、OCH₃、C₂H₅、OC₂H₅Or C (CH)₃)₃Any one of the above, 4,5, 6-trisubstituted phenylboronate, wherein the substituent group is any one of a neutral group, a group with electron donating property, or a group with electron withdrawing property, and the neutral group is H; groups of electron donating character include CH₃、OCH₃、C₂H₅、OC₂H₅And C (CH)₃)₃(ii) a Groups of electron-withdrawing character include F, CF₃CN and CHO.

Preferably, substance B is prepared by subjecting substance A to boration, substance A being 3- [10- (4-electron donating substitution) benzanthracene ] -4,5, 6-trisubstituted chlorobenzene; the method comprises the following specific steps: mixing 0.5-2 mmol of the substance A, 1.5-6 mmol of pinacol diboron, 0.05-0.2 mmol of palladium acetate, 0.1-0.4 mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 1.5-6 mmol of potassium acetate and 25-90 mL of 1,4-dioxane, vacuumizing the system, reacting at 95-105 ℃ for 12-18 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain the substance B.

Preferably, the substance A is obtained by Suzuki coupling reaction of 9- (4-powered substituted phenyl) -10 borate anthracene and 1-chloro-3-iodo-4, 5, 6-trisubstituted benzene, and the specific steps comprise: 9- (4-powered substituted phenyl) -10 borate anthracene, 1-chloro-3-iodo-4, 5, 6-trisubstituted benzene, tetrakis (triphenylphosphine) palladium, toluene, ethanol and K₂CO₃The solution is prepared according to the following (1-3) mmol: (1-3) mmol: (0.1-0.3) mmol: (40-120) mL: (10-30) mL: (40-120) and carrying out mmol mixing, reacting for 12-24 hours at 100-110 ℃ under the protection of nitrogen to obtain an intermediate product, extracting the intermediate product, carrying out rotary evaporation, carrying out column chromatography, and recrystallizing to obtain a substance A.

Preferably, the 9- (4-powered substituted phenyl) -10 borate anthracene is prepared by esterification of 9-bromo-10- (4-powered substituted) phenylanthracene boric acid, and specifically comprises the following steps: mixing 4.22-12.66 mmol of 9-bromo-10- (4-electron-donating substituted) phenylanthracene, 6.32-18.96 mmol of isopropoxy borate, 7.2-21.6 mmol of n-butyllithium (added at-78 ℃) and 50-150 mL of THF, reacting at room temperature for 8-12 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain 9- (4-electron-donating substituted phenyl) -10 borate anthracene.

Preferably, the 9-bromo-10- (4-electrokinetic substituted) phenylanthracene is obtained by brominating 9- (4-electrokinetic substituted) phenylanthracene, and the specific steps comprise: 9- (4-substituted) benzanthracene, N-bromosuccinimide and N, N-dimethylformamide are added according to the proportion of (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ under the atmosphere of nitrogen gas, washing with methanol, and performing suction filtration to obtain 9-bromo-10- (4-electrokinetic substitution);

the 9- (4-substituted) phenylanthracene is obtained by performing Suzuki coupling reaction on 9-bromoanthracene, and the specific preparation steps comprise: 9-bromoanthracene, 4-electro-substituted phenylboronic acid, tetrakis (triphenylphosphine) palladium, toluene, ethanol and K₂CO₃According to the weight ratio of (5-20) mmol: (7.5-30) mmol: (0.25-1) mmol: (50-200) mL: (15-60) mL: and (50-200) mmol, performing reflux reaction at 100-110 ℃ for 12-24 hours under the inert gas atmosphere, extracting, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain the 9- (4-electron supply substituted) phenylanthracene.

Preferably, the 9-bromo-10- (4-electroabsorption substituted) phenylanthracene is obtained by brominating 9- (4-electroabsorption substituted) phenylanthracene, and the method comprises the following specific steps: 9- (4-electro-absorption substituted) benzene anthracene, N-bromosuccinimide and N, N-dimethylformamide are added according to the proportion of (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ in an inert gas atmosphere, washing the reaction product with methanol, and performing suction filtration to obtain 9-bromo-10- (4-electroabsorption substituted) phenylanthracene;

the 9- (4-electro-absorption substituted) phenylanthracene is obtained by performing Suzuki coupling reaction on 9-bromoanthracene, and the specific preparation steps comprise: 9-bromoanthracene, 4-electroabsorption substituent phenylboronic acid, tetrakis (triphenylphosphine) palladium, toluene, ethanol and K₂CO₃According to the weight ratio of (5-20) mmol: (7.5-30) mmol: (0.25-1) mmol: (50-200) mL: (15-60) mL: and (50-200) mmol, carrying out reflux reaction at 100-110 ℃ for 12-24 hours in a nitrogen atmosphere, extracting after the reaction is finished, carrying out rotary evaporation, carrying out column chromatography, and recrystallizing to obtain the 9- (4-electro-absorption substituted) phenylanthracene.

Preferably, in the Suzuki coupling reaction, a catalyst, a solvent and an activating agent are also added; wherein the ratio of the substance B, 9-bromo-10- (4-electron-withdrawing substituted) phenylanthracene, the catalyst, toluene, ethanol and the activator is (0.25-1) mmol: (0.21-0.84) mmol: (0.03-0.12) mmol: (15-60) mL: (5-20) mmol: (8.4-33.6) mmol; the catalyst adopts tetrakis (triphenylphosphine) palladium; the activator adopts K₂CO₃A solution; the Suzuki coupling reaction is carried out under the nitrogen atmosphere at the temperature of 100-110 DEG CAnd reacting for 12-24 hours, and after the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product.

The application of the D-A type organic blue fluorescent material in an organic electroluminescent diode device.

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

the invention discloses a D-A type organic blue fluorescent material which is a dianthracene derivative and can realize deep blue light emission. According to the invention, benzene is used as a central pi-conjugated bridge chain, and two anthracene light-emitting units (one group with an electron-donating characteristic and one group with an electron-withdrawing characteristic) are respectively connected at the meta position of the benzene, so that the conjugated form of organic material molecules and the charge transfer path (ICT) in the molecules are regulated, the deep blue light emission of the material molecules is realized, and the balance of carrier injection in the application of an OLED device is realized. Meanwhile, groups with electron donating characteristics or electron withdrawing characteristics are introduced to the central benzene pi conjugated bridge chain, so that pi-pi accumulation among organic material molecules is effectively inhibited, and high luminescence quantum efficiency of the material is realized. Benzene is used as a central pi conjugated bridge chain, and two anthracene light-emitting units (a group with an electron supply characteristic and a group with an electron absorption characteristic) are respectively connected at the meta position of the benzene, so that the conjugated form and the intra-molecular charge transfer path of organic molecules are regulated and controlled, and the balance of deep blue emission of material molecules and carrier injection in OLED device application is realized; meanwhile, a steric hindrance group is introduced to the central pi conjugate bridge chain to eliminate pi-pi stacking interaction among organic material molecules, so that high luminescent quantum efficiency is realized; in the non-doped OLED device, the deep blue light emission is realized, the color purity is high, the performance is excellent, the manufacturing cost can be reduced, and the production process is simplified. In summary, the present invention is characterized in that: 1) benzene is used as a central pi-conjugated bridge chain, and two meta positions of the benzene are used for connecting two anthracene light-emitting units, so that the control of the conjugated state, excited state charge transfer and stacked state of an organic molecule and charge injection balance in the application of an OLED device is realized; 2) groups with electron donating characteristics or electron withdrawing characteristics are introduced to the central pi conjugated bridge chain to further inhibit pi-pi interaction between organic molecules, improve the luminous quantum efficiency of material molecules and realize deep blue emission.

The invention also discloses a preparation method of the D-A type organic blue fluorescent material, which takes benzene as a pi conjugated bridge chain, and two anthracene light-emitting units (one group with electron donating property and one group with electron withdrawing property) are respectively connected on the meta position of the benzene to realize the regulation and control of the conjugated state and excited state charge transfer path of organic molecules, further realize the injection balance of current carriers in the application of OLED devices, and simultaneously introduce a group with electron donating property or an electron withdrawing property on the central pi conjugated bridge chain to further inhibit the pi-pi interaction between the organic molecules, improve the luminous quantum efficiency of the material molecules, realize the emission of deep blue light, and successfully prepare the organic deep blue fluorescent material with good thermal stability and high fluorescence quantum efficiency; the whole synthesis steps are simple, the yield is high, and the materials are easy to purify.

The invention also discloses application of the D-A type organic blue fluorescent material in an organic electroluminescent diode device. Under the irradiation of ultraviolet light, the prepared organic blue fluorescent material has strong deep blue fluorescent emission in solution or film. The organic blue fluorescent material is taken as a main luminescent material, and a high-performance non-doped deep blue OLED device is successfully prepared; when the material is applied to the non-doped OLED, the EQE (about 3.66%) is far higher than the EQE value (about 0.6%) calculated theoretically, [ EQE ]_{Theory of the invention}＝η_eh·η_PL·η_exciton·η_out1 × 0.08 × 0.25 × 0.3 ═ 0.6% ], wherein η_ehIs the recombination rate of electrons and holes; eta_PLFluorescence quantum yield eta for clean membranes_excitonThe ratio of excitons; eta_outIs the light transmittance.

[ description of the drawings ]

FIG. 1 is a nuclear magnetic spectrum of an organic blue fluorescent material prepared in example 1 of the present invention.

FIG. 2 is a mass spectrum of the organic blue fluorescent material prepared in example 1 of the present invention.

FIG. 3 is a thermogravimetric plot of the anthracene derivative a obtained in examples 1-3 of the invention.

FIG. 4 shows absorption spectra of organic blue fluorescent materials prepared in example 1 of the present invention in different solutions.

FIG. 5 shows emission spectra of organic blue fluorescent materials prepared in example 1 of the present invention in different solutions.

FIG. 6 shows the absorption and emission spectra of the organic blue fluorescent material prepared in example 1 of the present invention on a thin film.

Fig. 7 is an Electroluminescence (EL) spectrum of the device 1 produced by the present invention.

Fig. 8 is a current density-voltage-luminance (Cd-V-L) profile curve for a device 1 made in accordance with the present invention.

Fig. 9 is a graph of current efficiency-current density-power efficiency (CE-Cd-PE) for the device 1 made in accordance with the present invention.

FIG. 10 is a plot of current density versus external quantum efficiency (Cd-EQE) for a device 1 made in accordance with the present invention.

[ detailed description ] embodiments

The invention is described in further detail below with reference to the figures and the specific steps:

the invention discloses a D-A type organic blue fluorescent material and a preparation method and application thereof; according to the invention, through precise design of material molecules, benzene is taken as a central pi-conjugated bridge chain, and two anthracene light-emitting units (a group with an electron-donating property and a group with an electron-withdrawing property) are respectively connected at the meta position of the benzene to regulate and control the conjugated state of organic molecules, an excited state charge transfer path and a pi-pi stacking effect among molecules, so that charge injection balance in deep blue emission and OLED device application is realized, and meanwhile, a group with an electron-donating property or an electron-withdrawing property is introduced into the central pi-conjugated bridge chain to further inhibit the pi-pi stacking effect among the organic molecules, so that efficient light emission of the material molecules is realized. The prepared organic blue fluorescent material has good thermal stability and high luminous quantum efficiency. The chemical structural formula is shown as follows.

Wherein R is₁Radicals for imparting electronic properties, R₂Radicals of electron-withdrawing character, R₃、R₄Being a neutral group or a group of electron donating nature or a group of electron withdrawing nature, the group of electron donating nature is preferably: CH (CH)₃、OCH₃、C₂H₅、OC₂H₅Or C (CH)₃)₃(ii) a The group having electron-withdrawing property is preferably F, CF₃CN or CHO; the neutral group is preferably H; the chemical structural formula of the synthesized organic blue fluorescent material is shown as follows:

the compound is compound a, compound b, compound c, compound d, compound e, compound f, compound g, compound h, compound i, compound j, compound m, compound n, compound o and compound p in turn; wherein the compound is R₁、R₂、R₃、R₄In any combination of (1), R represents a part of the above chemical formula₁、R₂、R₃And R₄Optional groups are detailed in table 1.

TABLE 1R₁、R₂、R₃And R₄Optional group of (1)

R₁	CH₃、OCH₃、C₂H₅、OC₂H₅Or C (CH)₃)₃
		R₂	F、CF₃CN or CHO
R₃、R₄	H、CH₃、OCH₃、C₂H₅、OC₂H₅、C(CH₃)₃、F、CF₃CN or CHO

The specific synthetic route of the organic blue fluorescent material of the invention is shown as the following formula (1):

2a in the above formula denotes

3a denotes

4a denotes

Corresponding 2b denotes

3b denotes

4b denotes

Taking the synthesis example of the compound a, the specific synthetic route is shown as the following formula (2):

taking the synthesis example of the compound b, the specific synthetic route is shown as the following formula (3):

the specific process of the synthesis process comprises the following steps:

step 1, Synthesis of groups with Electron donating Properties

Adding 5-20 mmol of 9-bromoanthracene, 7.5-30 mmol of 4-electrically supplied substituted phenylboronic acid (2a), 15-60 mL of potassium carbonate solution, 50-200 mL of toluene and 15-60 mL of ethanol into a reaction bottle, wherein the potassium carbonate solution is prepared by adding 50-200 mmol of potassium carbonate solid into 15-60 mL of water; and finally adding 0.25-1 mmol of tetrakis (triphenylphosphine) palladium. And then, vacuumizing the system, and refluxing for 12-24 hours at 100-110 ℃ under the protection of nitrogen. After the reaction is finished, extracting, rotary steaming, carrying out column chromatography, and recrystallizing to obtain 9- (4-electro-substituted) phenylanthracene (3 a); wherein any of the groups substituted by electron donating property includes CH₃、OCH₃、C₂H₅、OC₂H₅And C (CH)₃)₃。

(ii) bromination of 9- (4-substituted) benzanthracene: adding 2.50-10 mmol of 9- (4-powered substituted) (3a) phenylanthracene, 40-150 mL of N, N-Dimethylformamide (DMF) and 3-12 mmol of N-bromosuccinimide (NBS) into a reaction bottle, vacuumizing the system, reacting at 85-90 ℃ for 1-2 hours under the protection of nitrogen, washing the reaction product with methanol, and performing suction filtration to obtain 9-bromo-10- (4-powered substituted) phenylanthracene (4 a).

Step 2, synthesizing a group with electron-withdrawing property

Adding 5-20 mmol of 9-bromoanthracene, 7.5-30 mmol of 4-electro-absorption substituent phenylboronic acid (2b), 15-60 mL of potassium carbonate solution, 50-200 mL of toluene and 15-60 mL of ethanol into a reaction bottle, wherein the potassium carbonate solution is prepared by adding 50-200 mmol of potassium carbonate solid into 15-60 mL of water; and finally adding 0.25-1 mmol of tetrakis (triphenylphosphine) palladium. Then, the system is vacuumized and refluxed for 12 to 24 hours at the temperature of 100 to 110 ℃ under the protection of nitrogen. After the reaction is finished, extracting, rotary steaming, carrying out column chromatography, and recrystallizing to obtain 9- (4-electro-absorption substituted) phenylanthracene (3 b); wherein the electron-withdrawing substitution is any of groups having an electron-withdrawing property, including F, CF₃、CN、CHO。

(ii) bromination of 9- (4-electrophilic substitution) phenylanthracene: adding 2.50-10 mmol of 9- (4-electroabsorption substituted) phenylanthracene (3b), 40-150 mL of N, N-Dimethylformamide (DMF) and 3-12 mmol of N-bromosuccinimide (NBS) into a reaction bottle, vacuumizing the system, reacting for 1-2 hours at 85-90 ℃ under the protection of nitrogen, washing the reaction product with methanol, and performing suction filtration to obtain 9-bromo-10- (4-electroabsorption substituted) phenylanthracene (4 b).

Step 3, Synthesis of the end product

Boric acid esterification of 9-bromo-10- (4-substituted) phenylanthracene: 4.22-12.66 mmol of 9-bromo-10- (4-electro-substituted) phenylanthracene (4a) prepared in the step 1, 6.32-18.96 mmol of isopropoxy borate, 7.2-21.6 mmol of n-butyllithium (added at-78 ℃), and 50-150 mL of THF are added into a reaction bottle, and then the system is vacuumized and stirred at room temperature for 8-12 hours under the protection of nitrogen. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9- (4-power supply substituted phenyl) -10 boric acid ester anthracene (5 a).

② Suzuki coupling reaction of 9- (4-power supply substituted phenyl) -10 boric acid ester anthracene: 1-3 mmol of 9- (4-powered substituted phenyl) -10 borate anthracene (5a), 1-3 mmol of 1-chloro-3-iodo-4, 5, 6-trisubstituted benzene, 0.1-0.3 mmol of tetrakis (triphenylphosphine) palladium, 40-120 mL of toluene, 10-30 mL of ethanol and K₂CO₃Adding 40-120 mmol (prepared by dissolving in 10-30 mL of distilled water) of the solution into a reaction bottle, vacuumizing the system, reacting for 12-24 hours at 100-110 ℃ under the protection of nitrogen, extracting, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain a product A, 3- [10- (4-power supply substitution) phenylanthracene]-4,5, 6-trisubstituted chlorobenzenes; the substituent group in the 1-chloro-3-iodo-4, 5, 6-trisubstituted benzene is R₃、R₄，R₃And R₄Is any one of groups with electron donating property or any one of groups with electron withdrawing property or a neutral group, and the neutral group is H; groups of electron donating character include CH₃、OCH₃、C₂H₅、OC₂H₅And C (CH)₃)₃(ii) a Groups of electron-withdrawing character include F, CF₃CN and CHO.

③ boric acid esterification reaction of A: mixing 0.5-2 mmol of A, 1.5-6 mmol of pinacol diboron diborate, 0.05-0.2 mmol of palladium acetate, 0.1-0.4 mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl (S-Phos), 1.5-6 mmol of potassium acetate (KOAc) and 25-90 mL of 1,4-dioxane (1,4-dioxane), adding into a reaction bottle, vacuumizing the system, reacting at 95-105 ℃ for 12-18 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain a substance B;

the product B is 3- [10- (4-substituted) benzanthracene ] -4,5, 6-trisubstituted phenylboronate, wherein the 4,5, 6-trisubstituted phenyl is 5-methyl-4, 6-dihydrophenyl, 5-fluoro-4, 6-dihydrophenyl, 5-methoxy-4, 6-dihydrophenyl, 5-ethyl-4, 6-dihydrophenyl, 5-ethoxy-4, 6-dihydrophenyl, 5-tert-butyl-4, 6-dihydrophenyl, 5-cyano-4, 6-dihydrophenyl, 5-trifluoromethyl-4, 6-dihydrophenyl, 5-hydro-4, 6-dimethoxyphenyl, 5-hydro-4, 6-dimethylphenyl, 5-hydro-4, 6-dialdehyde-phenyl, 5-hydro-4, 6-dicyanophenyl, 4,5, 6-trihydrophenyl, 4,5, 6-trimethoxyphenyl, 4,5, 6-trimethylphenyl or 4,5, 6-trifluorophenyl.

The 4,5, 6-trisubstituted phenyl group is only a part thereof, and the trisubstitution may be any one of an electron donating stituent, an electron withdrawing stituent or a neutral group.

Synthesis of final product: 0.25-1 mmol of the substance B, 0.21-0.84 mmol of the product 4B obtained in the step 2, namely 9-bromo-10- (4-electroabsorption substituted) phenylanthracene, 0.03-0.12 mmol of palladium tetrakis (triphenyl) phosphine, 15-60 mL of toluene, 5-20 mL of ethanol and K₂CO₃8.4-33.6 mmol (5-20 mL of distilled water is used for preparing a solution), adding into a reaction bottle, and refluxing for 12-24 hours at 100-110 ℃ under the protection of nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product which is an organic blue fluorescent material.

The potassium carbonate solution is added to activate the borate ions and convert them to reactive intermediates. Ethanol is added to increase the hydrophilicity of the solvent and to allow the reaction to proceed under homogeneous conditions.

Intermediate A in the following examples₁～A₁₆Is represented by R₃、R₄Different groups and different intermediates synthesized, B₁～B₁₆The same is true.

Example 1

Step 1, synthesizing a group with electron donating property: adding 5mmol of 9-bromoanthracene, 7.5mmol of 4-methoxyphenylboronic acid, 50mmol of potassium carbonate solution (prepared into solution by using 15mL of distilled water), 50mL of toluene and 15mL of ethanol into a reaction bottle, and finally adding 0.25mmol of tetrakis (triphenylphosphine) palladium. Then the system is vacuumized and refluxed for 12 hours at 100 ℃ under the protection of nitrogen. After the reaction is finished, extraction, rotary evaporation, column chromatography (eluent: n-hexane/dichloromethane ═ 4:1) and recrystallization are carried out to obtain 9- (4-methoxy) phenylanthracene. The yield was 86%. ② adding 2.50mmol of 9- (4-methoxy) phenylanthracene, 40mL of N, N-Dimethylformamide (DMF) and 3mmol of N-bromosuccinimide (NBS) into a reaction bottle, then vacuumizing the system, and reacting for 1 hour at 85 ℃ under the protection of nitrogen. Washing with methanol, and performing suction filtration to obtain the product 9-bromo-10- (4-methoxy) phenylanthracene with the yield of 89%.

Step 2, synthesizing a group with electron-withdrawing property: the same step 1[ only need to replace 4-methoxyphenylboronic acid and 9- (4-methoxy) phenylanthracene in (r) to 4-cyanophenylboronic acid and 9- (4-cyano) phenylanthracene ].

Step 3, the synthesis process of the final product: 4.22mmol of 9-bromo-10- (4-methoxy) phenylanthracene, 6.32mmol of isopropoxy borate, 7.2mmol of n-butyllithium (added at-78 ℃) and 50mL of THF are added into a reaction bottle, and then the system is vacuumized and stirred at room temperature for 8 hours under the protection of nitrogen. After the reaction is finished, extracting, rotary evaporating, carrying out column chromatography (eluent: n-hexane/dichloromethane ═ 2:1), and recrystallizing to obtain the product 9- (4-methoxy) -10 boronic acid ester anthracene. The yield was 80%. ② 1mmol of 9- (4-methoxy) -10 borate anthracene, 1mmol of 1-chloro-3-iodo-4, 5, 6-trihydrogen substituted benzene, 0.1mmol of tetrakis (triphenylphosphine) palladium, 40mL of toluene, 10mL of ethanol and K₂CO₃Adding 40mmol (10 mL of distilled water to prepare solution) into a reaction bottle, vacuumizing the system, protecting with nitrogen, and performing vacuum evaporation and vacuum evaporation on the system by 10mmolReacting at 0 deg.C for 12 hr, extracting, rotary evaporating, column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain product A₁. The yield was 68%. ③ A₁0.5mmol, 1.5mmol of pinacol ester diborate, 0.05mmol of palladium acetate, 0.1mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 1.5mmol of potassium acetate and 25mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, protected by nitrogen, reacted at 90 ℃ for 12 hours, after the reaction is finished, extracted, evaporated, subjected to column chromatography (eluent: n-hexane/dichloromethane ═ 2:1), and recrystallized to obtain a product B₁. The yield was 70%. Fourthly, obtaining a final product a through Suzuki coupling reaction: b is to be₁0.25mmol, 0.21mmol of the product obtained in step 2, namely 9-bromo-10- (4-cyano) phenylanthracene, 0.03mmol of catalyst tetrakis (triphenyl) phosphine palladium, 15mL of toluene, 5mL of ethanol and K₂CO₃8.4mmol (dissolved in 5mL of distilled water), added to a reaction flask, and refluxed at 100 ℃ for 12h under the protection of nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 78%. Nuclear magnetic resonance analysis: NMR (400MHz,)¹H NMR (400MHz,) δ 8.04-7.92 (m,2H),7.86(d, J ═ 7.7,1H),7.75(d, J ═ 8.4,1H),7.61(s,1H),7.53(d, J ═ 8.5,1H), 7.48-7.30 (m,5H),7.25(s,4H),3.95(s,2H),1.56(s,7H), a nuclear magnetic spectrum, as shown in fig. 1 below. Mass spectrum (m/s) with molecular formula C₄₈H₃₁NO, theoretical 637.24 and actual 637, mass spectra as shown in FIG. 2 below.

Example 2

Step 1 synthesis of groups that supply electronic properties: 10mmol of 9-bromoanthracene, 15mmol of 4-methoxyphenylboronic acid, 100mmol of potassium carbonate solution (prepared into solution by using 30mL of distilled water), 136mL of toluene and 30mL of ethanol are added into a reaction bottle, and finally 0.5mmol of tetrakis (triphenylphosphine) palladium is added. The system was then evacuated and refluxed at 105 f for 18 hours under nitrogen. After the reaction is finished, extraction, rotary evaporation, column chromatography (eluent: n-hexane/dichloromethane ═ 4:1) and recrystallization are carried out to obtain 9- (4-methoxy) phenylanthracene. The yield was 90%. ② adding 5mmol of 9- (4-methoxy) phenylanthracene, 75mL of N, N-Dimethylformamide (DMF) and 6mmol of N-bromosuccinimide (NBS) into a reaction bottle, and then vacuumizing the system to react for 1.5 hours at 88 ℃ under the protection of nitrogen. Washing with methanol, and performing suction filtration to obtain the product 9-bromo-10- (4-methoxy) phenylanthracene with the yield of 89%.

Step 3, the synthesis process of the final product: carrying out the next step on the basis of the step 1, adding 8.44mmol of 9-bromo-10- (4-methoxy) phenylanthracene, 12.64mmol of isopropoxy borate, 14.4mmol of n-butyl lithium (added at-78 ℃), and THF100mL into a reaction bottle, vacuumizing the system, and stirring at room temperature for 10 hours under the protection of nitrogen. After the reaction is finished, extraction, rotary evaporation, column chromatography (eluent: n-hexane/dichloromethane ═ 2:1) and recrystallization are carried out to obtain the product 9- (4-methoxy) -10 boronic acid ester anthracene with the yield of 70%. ② 2mmol of 9- (4-methoxy) -10 borate anthracene, 2mmol of 1-chloro-3-iodo-4, 5, 6-trihydrogen substituted benzene, 0.2mmol of tetrakis (triphenylphosphine) palladium, 80mL of toluene, 20mL of ethanol and K₂CO₃Adding 80mmol (prepared into solution by 20mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 100 ℃ for 12 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₁. The yield was 69%. ③ A₁Adding 1mmol, 3mmol of diboron pinacol ester, 0.1mmol of palladium acetate, 0.2mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 3mmol of potassium acetate and 45mL of 1,4-dioxane into a reaction bottle, vacuumizing the system, reacting at 95 ℃ for 16 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 2:1), and recrystallizing to obtain a product B₁. The yield was 65%. Fourthly, obtaining a final product a through Suzuki coupling reaction: b is to be₁0.5mmol, 0.42mmol of the product obtained in step 2, namely 9-bromo-10- (4-cyano) phenylanthracene, 0.06mmol of catalyst tetrakis (triphenyl) phosphine palladium, 30mL of toluene, 10mL of ethanol and K₂CO₃16.8mmol (dissolved in 10mL of distilled water) was added to the flask and refluxed at 105 ℃ for 18h under nitrogen. After the reaction is finished, hot washing with methanol, suction filtration, recrystallization with toluene and sublimationThe final product is obtained. The yield was 75%. Molecular formula C₄₈H₃₁NO, theoretical value 637.24, actual value 637.

Example 3

Step 1 synthesis of groups that supply electronic properties: 20mmol of 9-bromoanthracene, 30mmol of 4-methoxyphenylboronic acid, 200mmol of potassium carbonate solution (prepared into solution by using 60mL of distilled water), 200mL of toluene and 60mL of ethanol are added into a reaction bottle, and finally 1mmol of tetrakis (triphenylphosphine) palladium is added. Then the system is vacuumized and refluxed for 24 hours at 110 ℃ under the protection of nitrogen. After the reaction is finished, extraction, rotary evaporation, column chromatography (eluent: n-hexane/dichloromethane ═ 4:1) and recrystallization are carried out to obtain 9- (4-methoxy) phenylanthracene. The yield was 89%. ② adding 10mmol of 9- (4-methoxy) benzanthracene, 150mL of N, N-Dimethylformamide (DMF) and 12mmol of N-bromosuccinimide (NBS) into a reaction bottle, then vacuumizing the system, and reacting for 2 hours at 90 ℃ under the protection of nitrogen. Washing with methanol, and performing suction filtration to obtain the product 9-bromo-10- (4-methoxy) phenylanthracene with the yield of 90%.

Step 3, the synthesis process of the final product: carrying out the next step on the basis of the step 1, adding 12.66mmol of 9-bromo-10- (4-methoxy) phenylanthracene, 18.96mmol of isopropoxy borate, 21.60mmol of n-butyl lithium (added at-78 ℃), and THF150mL into a reaction bottle, vacuumizing the system, and stirring at room temperature for 12 hours under the protection of nitrogen. After the reaction is finished, extraction, rotary evaporation and column chromatography (eluent: n-hexane/dichloromethane ═ 2:1) are carried out, and the product 9- (4-methoxy) -10 boronic acid ester anthracene is obtained by recrystallization with the yield of 68%. ② 3mmol of 9- (4-methoxy) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-4, 5, 6-trihydrogen substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₁. Yield of66 percent. ③ A₁2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₁Yield 68%. Fourthly, obtaining a final product a through Suzuki coupling reaction: b is to be₁1mmol, 0.84mmol of the product obtained in step 2, namely 9-bromo-10- (4-cyano) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 78%. Molecular formula C₄₈H₃₁NO, theoretical value 637.24, actual value 637.

Example 4

(ii) Steps 1,2 and 3 are the same as in example 3.

② 3mmol of 9- (4-methoxy) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-methyl-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₂. The yield was 66%. ③ A₂2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₂Yield 68%. Fourthly, obtaining a final product b through Suzuki coupling reaction: b is to be₂1mmol, the product obtained in step 2 is 9-bromine0.84mmol of-10- (4-cyano) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 68%. Molecular formula C₄₉H₃₃NO, theoretical value 651.26, actual value 651.

Example 5

(ii) Steps 1,2 and 3 are the same as in example 3.

② 3mmol of 9- (4-methoxy) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-fluoro-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₃. The yield was 66%. ③ A₃2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₃Yield 68%. Fourthly, obtaining a final product c through Suzuki coupling reaction: b is to be₃1mmol, 0.84mmol of the product obtained in step 2, namely 9-bromo-10- (4-cyano) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 69%. Molecular formula C₄₈H₃₀FNO, theoretical 655.23, actual 655.

Example 6

(ii) Steps 1,2 and 3 are the same as in example 3. (only need to replace 4-methoxyphenylboronic acid and 4-cyanophenylboronic acid in the step 1 and the step 2 with 4-methylphenylboronic acid and 4-fluorophenylboronic acid respectively).

② 3mmol of 9- (4-methyl) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-methoxy-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₄. The yield was 66%. ③ A₄2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₄Yield 68%. Fourthly, obtaining a final product d through Suzuki coupling reaction: b is to be₄1mmol, 0.84mmol of the product obtained in step 2, namely 9-bromo-10- (4-fluoro) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 70%. Molecular formula C₄₈H₃₃FO, theoretical 644.25 and actual 644.

Example 7

The procedure in

Steps

1,2 and 3 was the same as in example 6. (only the 4-fluorobenzeneboronic acid in the step 2 needs to be replaced by the 4-trifluorophenylboronic acid).

② 3mmol of 9- (4-methyl) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-ethyl-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution with 30mL distilled water) into a reaction flask, vacuumizing the system, and keeping nitrogenProtecting, reacting at 110 ℃ for 24 hours, extracting after the reaction is finished, rotary evaporating, carrying out column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain the product A₅. The yield was 66%. ③ A₅2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₅Yield 68%. Fourthly, obtaining a final product e through Suzuki coupling reaction: b is to be₅1mmol, 0.84mmol of the product obtained in step 2, namely 9-bromo-10- (4-trifluoro) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 70%. Molecular formula C₅₀H₃₅F₃The theoretical value is 692.27, and the actual value is 692.

Example 8

The procedure in

Steps

1,2 and 3 was the same as in example 6. (only need to replace 4-methylphenylboronic acid in the (1) step with 4-ethylphenylboronic acid, respectively).

② 3mmol of 9- (4-ethyl) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-ethoxy-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₆. The yield was 68%. ③ A₆2mmol, 6mmol of biboronic acid pinacol ester, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl and 6mmol of potassium acetate, and 90mL of 1,4-dioxane are added into a reaction bottle, and then the system is vacuumized, protected by nitrogen, and reacted at 105 ℃ for 18H, after the reaction is finished, extracting, rotary evaporating, carrying out column chromatography (eluent: n-hexane/dichloromethane ═ 2:1), and recrystallizing to obtain a product B₆Yield 68%. Fourthly, obtaining a final product f through Suzuki coupling reaction: b is to be₆1mmol, 0.84mmol of the product obtained in step 2, namely 9-bromo-10- (4-fluoro) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 66%. Molecular formula C₅₀H₃₇FO, theoretical 672.28 and actual 672.

Example 9

(ii) Steps 1,2 and 3 are the same as in example 3. (only need to replace 4-methoxyphenylboronic acid and 4-cyanophenylboronic acid in the step 1 and the step 2 with 4-ethoxyphenylboronic acid and 4-aldehyde phenylboronic acid respectively).

② 3mmol of 9- (4-ethoxy) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-tert-butyl-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₇. The yield was 66%. ③ A₇2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₇Yield 68%. Fourthly, obtaining a final product g through Suzuki coupling reaction: b is to be₇1mmol, 0.84mmol of the product obtained in the step 2, namely 9-bromo-10- (4-aldehyde) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (using)20mL of distilled water to prepare a solution), adding the solution into a reaction bottle, and refluxing for 24 hours at 110 ℃ under the protection of nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 70%. Molecular formula C₄₉H₃₃O₂The theoretical value is 653.25, and the actual value is 653.

Example 10

The procedure of

Steps

1,2 and 3 was the same as in example 9. (only the 4-ethoxyphenylboronic acid in (r) of step 1 needs to be replaced by 4-tert-butylboronic acid).

② 3mmol of 9- (4-tert-butyl) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-cyano-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₈. The yield was 66%. ③ A₈2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₈Yield 68%. Fourthly, obtaining a final product h through Suzuki coupling reaction: b is to be₈1mmol, 0.84mmol of the product obtained in the step 2, namely 9-bromo-10- (4-aldehyde) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 68%. Molecular formula C₄₈H₂₈NO, theoretical 634.22, actual 634.

Example 11

(ii) Steps 1,2 and 3 are the same as in example 3.

② 3mmol of 9- (4-methoxy) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-5-trifluoromethyl-4, 6-dihydro substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₉. The yield was 69%. ③ A₉2mmol, 6mmol of pinacol ester diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 18 hours at 105 ℃ under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₉Yield 68%. Fourthly, obtaining a final product i through Suzuki coupling reaction: b is to be₉1mmol, 0.84mmol of the product obtained in step 2, namely 9-bromo-10- (4-cyano) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, carrying out hot washing and suction filtration on methanol, recrystallizing toluene, and sublimating to obtain a final product. The yield was 69%. Molecular formula C₄₉H₃₀F₃NO, theoretical 705.23, actual 705.

Example 12

(ii) Steps 1,2 and 3 are the same as in example 3.

② 3mmol of 9- (4-methoxy) -10 borate anthracene, 3mmol of 1-chloro-3-iodo-4, 6-dimethoxy-5-hydrogen substituted benzene, 0.3mmol of tetrakis (triphenylphosphine) palladium, 120mL of toluene, 30mL of ethanol and K₂CO₃Adding 120mmol (prepared into solution by using 30mL of distilled water) into a reaction bottle, vacuumizing the system, reacting at 110 ℃ for 24 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography (eluent: n-hexane/dichloromethane ═ 1:1), and recrystallizing to obtain a product A₁₀. The yield was 69%. ③ A₁₀2mmol，6mmol of pinacol diboron, 0.2mmol of palladium acetate, 0.4mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 6mmol of potassium acetate and 90mL of 1,4-dioxane are added into a reaction bottle, then the system is vacuumized, the reaction is carried out at 105 ℃ for 18 hours under the protection of nitrogen, after the reaction is finished, the extraction, the rotary evaporation and the column chromatography are carried out (eluent: n-hexane/dichloromethane ═ 2:1), and the product B is obtained by recrystallization₁₀Yield 68%. Fourthly, obtaining a final product j through Suzuki coupling reaction: b is to be₁₀1mmol, 0.84mmol of the product obtained in step 2, namely 9-bromo-10- (4-cyano) phenylanthracene, 0.12mmol of catalyst tetrakis (triphenyl) phosphine palladium, 60mL of toluene, 20mL of ethanol and K₂CO₃33.6mmol (dissolved in 20mL of distilled water) was added to the reaction flask and refluxed at 110 ℃ for 24h under nitrogen. After the reaction is finished, hot washing and suction filtering are carried out on methanol, and the final product is obtained by toluene recrystallization and sublimation. The yield was 69%. Molecular formula C₅₀H₃₅NO₃The theoretical value is 697.26, and the actual value is 697.

Example 13

The same as in example 12. (only 1-chloro-3-iodo-4, 6-dimethoxy-5-hydro substituted benzene in the second step of the step 3 needs to be replaced by 1-chloro-3-iodo-4, 6-dimethyl-5-hydro substituted benzene, and the functional group to be replaced is correspondingly replaced in the following steps.) the final product of the synthesis is k.

Example 14

The same as in example 12. (only 1-chloro-3-iodo-4, 6-dimethoxy-5-hydrogen substituted benzene in the second step of the step 3 needs to be replaced by 1-chloro-3-iodo-4, 6-dicarboxyl-5-hydrogen substituted benzene, and the functional group to be replaced is correspondingly replaced in the following steps.) the final product of the synthesis is l.

Example 15

The same as in example 12. (only 1-chloro-3-iodo-4, 6-dimethoxy-5-hydrogen substituted benzene in the second step of the step 3 needs to be replaced by 1-chloro-3-iodo-4, 6-dicyano-5-hydrogen substituted benzene, so that the functional group to be replaced is correspondingly replaced in the following steps.) the final product of the synthesis is m.

Example 16

(ii) Steps 1,2 and 3 are the same as in example 3. (only 1-chloro-3-iodo-4, 5, 6-trihydrogen substituted benzene in the second step of step 3 needs to be replaced by 1-chloro-3-iodo-4, 5, 6-trimethoxy substituted benzene, and the functional group to be replaced is correspondingly replaced in the following steps.) the final product of the synthesis is n.

Example 17

(ii) Steps 1,2 and 3 are the same as in example 3. (only 1-chloro-3-iodo-4, 5, 6-trihydrogen substituted benzene in the second step of step 3 needs to be replaced by 1-chloro-3-iodo-4, 5, 6-trimethyl substituted benzene, and the functional group to be replaced is also replaced correspondingly in the following steps.) the final product of the synthesis is o.

Example 18

(ii) Steps 1,2 and 3 are the same as in example 3. (only 1-chloro-3-iodo-4, 5, 6-trihydrogen substituted benzene in the second step of step 3 needs to be replaced by 1-chloro-3-iodo-4, 5, 6-trifluoro substituted benzene, and the functional group to be replaced is correspondingly replaced in the following steps.) the final product of the synthesis is p.

The above examples are only the synthesis steps of a part of the compounds of the present invention, R₁、R₂、R₃、R₄Can be any one of table 1, corresponding any combination; when R is₁When different, the 4-electron donating substituted phenylboronic acid used in the synthesis of the group having electron donating property in step 1 has different electron donating substitution, and can be CH₃、OCH₃、C₂H₅、OC₂H₅Or C (CH)₃)₃Any one of (a); when R is₂When the substitution by electron-withdrawing is different, the substitution by electron-withdrawing in the 4-electron-withdrawing phenylboronic acid used in the synthesis of the group having electron-withdrawing properties in step 2 can be F, CF₃Any one of CN and CHO; when R is₃Or R₄When different, the trisubstitution in the 1-chloro-3-iodo-4, 5, 6-trisubstituted benzene in the second step in the step 3 is different, and the substituent group is R₃、R₄，R₃And R₄Is any one of a neutral group or a group of electron donating property or any one of a group of electron withdrawing property, R₃And R₄Can be H or CH₃、OCH₃、C₂H₅、OC₂H₅、C(CH₃)₃、F、CF₃Any one of CN and CHO.

Through tests, the thermogravimetric graphs of the target product a of the above examples 1-3 are shown in figure 3, and the thermal decomposition temperature of a can be found to be 438 ℃ from the thermogravimetric graphs, which indicates that the material a has good thermal stability.

The target product a of examples 1-3 above was tested in cyclohexane, toluene and 1, 2-dichloroethane solutions (. about.10)^-6mol L^-1) And ultraviolet absorption and fluorescence emission spectra on thin films: FIGS. 4 and 5 show absorption and emission spectra of organic blue fluorescent materials prepared in examples 1 to 3, respectively, in different solutions; FIG. 6 shows the absorption (squares) and emission (circles) spectra of the organic blue phosphors prepared in examples 1-3, respectively, in the thin film: as can be seen from FIG. 4, the absorption peaks of a in different solvents are 354/374/396 nm, 357/377/398 nm and 358/378/399nm, and the peaks are characteristic absorption peaks from anthracene. The polarity of the solvent is not changed greatly from small to large, which shows that the dipole moment of the molecular ground state is changed slightly. It can be derived from fig. 5 that the emission peaks of a in different solvents are 418, 425, 427nm, respectively, with a red-shift phenomenon with increasing polarity of the solvent and a gradual decrease of the shoulder due to the change of dipole moment in the molecule in the excited state. As can be seen from FIG. 6, the absorption and emission peaks of a are 362/383/405 and 440nm, respectively, which are characteristic absorption and emission peaks derived from anthracene.

Application example 1

Preparation of organic electroluminescent device 1

This example prepares an organic electroluminescent device 1 according to the following method:

a) cleaning of ITO (indium tin oxide) glass: ultrasonically cleaning ITO glass by using a detergent, deionized water, THF (tetrahydrofuran) and an isopropanol solvent respectively for 20 minutes, and then treating the ITO glass in a plasma cleaner for 10 minutes, wherein the sheet resistance is 15-20 omega/sq;

b) vacuum evaporating a hole transport layer NPB on the anode ITO glass, wherein the thickness of the hole transport layer NPB is 30 nm;

c) an electron blocking layer TCTA was vacuum-deposited on the hole transport layer NPB to a thickness of 10 nm.

d) Vacuum evaporating a luminescent layer compound a on the electron blocking layer TCTA, wherein the thickness of the luminescent layer compound a is 20 nm;

e) TPBi as an electron transport layer is evaporated on the luminescent layer in vacuum, and the thickness is 40 nm;

f) vacuum evaporating an electron injection layer LiF on the electron transport layer, wherein the thickness of the electron injection layer LiF is 1 nm;

g) on the electron injection layer, cathode Al was vacuum-evaporated to a thickness of 100 nm.

The organic electroluminescent element 1 has a structure of ITO (110 nm)/NPB (30nm)/TCTA (10nm)/EML: [ a (20nm) ]/TPBi (40nm)/LiF (1nm)/Al (100nm) which are sequentially stacked.

The molecular structural formula of the material used in the device 1 (the light-emitting layer is the compound a) is shown in the following table 2:

TABLE 2 molecular structural formula of material used for device 1

Through tests, the luminescence (EL) map, the current density-voltage-brightness (Cd-V-L) map curve, the current density-current efficiency (Cd-CE-PE), and the current density-external quantum efficiency (Cd-EQE) map curves of the device 1 are respectively shown in fig. 7, fig. 8, fig. 9, and fig. 10: from fig. 7, it can be derived that: the device 1 is luminescent from material m and has a spectrum that does not change at different current densities, indicating its good stability of the electroluminescence spectrum. From fig. 9, it can be derived that the maximum current efficiency of the device 1 is 4.02Cd/a, as derived from fig. 9, 10: the efficiency roll-off of the device 1 is small, which indicates that the efficiency stability of the device is good.

The optoelectronic performance parameters of device 1 are shown in Table 3 below

TABLE 3 optoelectronic parameters of the electroluminescent device 1

In the above table, [ a ] device name, [ b ] light emitting layer, [ c ] represents lighting voltage, [ d ] represents maximum current efficiency, [ e ] represents maximum power efficiency, [ f ] represents maximum external quantum efficiency, [ g ] represents maximum external quantum efficiency at 500cd/a, [ h ] represents color purity Coordinate (CIE).

The organic device based on the material provided by the invention has the advantages that the lighting voltage is 3.6V, the y value of the chromaticity coordinate CIE is 0.14, and the low-voltage driven non-doped deep blue OLED device is realized. The organic light-emitting device of the present invention can be used in light sources such as electrophotographic photoreceptors, flat panel displays, copiers, printers, liquid crystal display backlights, and timers, as well as various light-emitting devices, various display devices, various signs, various sensors, various house numbers, and the like.

The material prepared by the invention has the characteristics of simple synthesis steps, low cost, high yield, easy purification and the like, and shows strong deep blue fluorescence emission in a solution or film state. The material prepared by the invention is applied to an OLED device, the deep blue light emission is realized, and the maximum EQE reaches 3.66%. The material prepared by the invention has certain application value and market prospect in the fields of organic display, organic solid illumination and the like.

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

1. A D-A type organic blue fluorescent material is characterized in that: the structural formula is as follows:

wherein: r₁Refers to a group of electron donating character, R₂Radicals indicating electron-withdrawing character, R₃、R₄Refers to a neutral group;

wherein R is₁Is OCH₃；R₂Is CN; r₃、R₄Is H;

adopting a substance B and 9-bromine-10- (4-electron-withdrawing substitution) phenylanthracenePrepared by the coupling reaction of the sycamore, and the substance B is 3- [10- (4-electron donating substitution) phenylanthracene]-4,5, 6-trisubstituted phenylboronate; wherein the electron-withdrawing substitution in the 9-bromo-10- (4-electron-withdrawing substitution) phenylanthracene is CN; 3- [10- (4-Electron donating substituted) benzanthracene]-4,5, 6-trisubstituted phenylboronic acid ester with electron substitution of OCH₃The substituent group in the 4,5, 6-trisubstituted phenylboronate is a neutral group, and the neutral group is H.

2. A method for preparing the D-a type organic blue fluorescent material according to claim 1, wherein: prepared by Suzuki coupling reaction of a substance B and 9-bromo-10- (4-electron-withdrawing substitution) phenylanthracene, wherein the substance B is 3- [10- (4-electron-donating substitution) phenylanthracene]-4,5, 6-trisubstituted phenylboronate; wherein the electron-withdrawing substitution in the 9-bromo-10- (4-electron-withdrawing substitution) phenylanthracene is CN; 3- [10- (4-Electron donating substituted) benzanthracene]-4,5, 6-trisubstituted phenylboronic acid ester with electron substitution of OCH₃The substituent group in the 4,5, 6-trisubstituted phenylboronic acid ester is a neutral group, and the neutral group is H;

the substance B is prepared by boric acid esterification of the substance A, and the substance A is 3- [10- (4-electron donating substitution) phenylanthracene ] -4,5, 6-trisubstituted chlorobenzene; the method comprises the following specific steps: mixing 0.5-2 mmol of the substance A, 1.5-6 mmol of pinacol diboron, 0.05-0.2 mmol of palladium acetate, 0.1-0.4 mmol of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl, 1.5-6 mmol of potassium acetate and 25-90 mL of 1,4-dioxane, vacuumizing the system, reacting at 95-105 ℃ for 12-18 hours under the protection of nitrogen, extracting, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain a substance B;

the 9-bromo-10- (4-electroabsorption substituted) phenylanthracene is obtained by brominating 9- (4-electroabsorption substituted) phenylanthracene, and the specific steps comprise: 9- (4-electro-absorption substituted) benzene anthracene, N-bromosuccinimide and N, N-dimethylformamide are added according to the proportion of (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ in an inert gas atmosphere, washing the reaction product with methanol, and performing suction filtration to obtain 9-bromo-10- (4-electroabsorption substituted) phenylanthracene;

the 9- (4-electro-absorption substituted) phenylanthracene is obtained by performing Suzuki coupling reaction on 9-bromoanthracene, and the specific preparation steps comprise: 9-bromoanthracene,4-electroattractive substituents phenylboronic acid, tetrakis (triphenylphosphine) palladium, toluene, ethanol and K₂CO₃According to the weight ratio of (5-20) mmol: (7.5-30) mmol: (0.25-1) mmol: (50-200) mL: (15-60) mL: and (50-200) mmol, carrying out reflux reaction at 100-110 ℃ for 12-24 hours in a nitrogen atmosphere, extracting after the reaction is finished, carrying out rotary evaporation, carrying out column chromatography, and recrystallizing to obtain the 9- (4-electro-absorption substituted) phenylanthracene.

3. The method for preparing D-A type organic blue fluorescent material according to claim 2, wherein: the substance A is obtained by performing Suzuki coupling reaction on 9- (4-power supply substituted phenyl) -10 borate anthracene and 1-chloro-3-iodo-4, 5, 6-trisubstituted benzene, and comprises the following specific steps: 9- (4-powered substituted phenyl) -10 borate anthracene, 1-chloro-3-iodo-4, 5, 6-trisubstituted benzene, tetrakis (triphenylphosphine) palladium, toluene, ethanol and K₂CO₃The solution is prepared according to the following (1-3) mmol: (1-3) mmol: (0.1-0.3) mmol: (40-120) mL: (10-30) mL: (40-120) and carrying out mmol mixing, reacting for 12-24 hours at 100-110 ℃ under the protection of nitrogen to obtain an intermediate product, extracting the intermediate product, carrying out rotary evaporation, carrying out column chromatography, and recrystallizing to obtain a substance A.

4. The method for preparing D-A type organic blue fluorescent material according to claim 3, wherein: the 9- (4-powered substituted phenyl) -10 borate anthracene is prepared by esterifying 9-bromo-10- (4-powered substituted) phenylanthracene boric acid, and specifically comprises the following steps: mixing 4.22-12.66 mmol of 9-bromo-10- (4-electro-substituted) phenylanthracene, 6.32-18.96 mmol of isopropoxy borate, 7.2-21.6 mmol of n-butyllithium and 50-150 mL of THF, reacting at room temperature for 8-12 hours under the protection of nitrogen, extracting after the reaction is finished, performing rotary evaporation, performing column chromatography, and recrystallizing to obtain 9- (4-electro-substituted phenyl) -10-boronate anthracene.

5. The method for preparing D-A type organic blue fluorescent material according to claim 4, wherein: the 9-bromo-10- (4-powered substituted) phenylanthracene is obtained by brominating 9- (4-powered substituted) phenylanthracene, and the specific steps comprise: 9- (4-substituted) benzanthracene, N-bromosuccinimide and N, N-dimethylformamide are added according to the proportion of (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ under the atmosphere of nitrogen gas, washing with methanol, and performing suction filtration to obtain 9-bromo-10- (4-electrokinetic substitution);

6. The method for preparing D-A type organic blue fluorescent material according to claim 2, wherein: in the suzuki coupling reaction, a catalyst, a solvent and an activating agent are also added; wherein the ratio of the substance B, 9-bromo-10- (4-electron-withdrawing substituted) phenylanthracene, the catalyst, toluene, ethanol and the activator is (0.25-1) mmol: (0.21-0.84) mmol: (0.03-0.12) mmol: (15-60) mL: (5-20) mmol: (8.4-33.6) mmol; the catalyst adopts tetrakis (triphenylphosphine) palladium; the activator adopts K₂CO₃A solution; the Suzuki coupling reaction is carried out for 12-24 hours at 100-110 ℃ under the nitrogen atmosphere, and after the reaction is finished, the final product is obtained by methanol hot washing, suction filtration, toluene recrystallization and sublimation.

7. Use of a D-a type organic blue fluorescent material according to claim 1 in an organic electroluminescent diode device.