CN109503427B - D-A type organic blue fluorescent material and preparation method and application thereof - Google Patents
D-A type organic blue fluorescent material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109503427B CN109503427B CN201811619632.0A CN201811619632A CN109503427B CN 109503427 B CN109503427 B CN 109503427B CN 201811619632 A CN201811619632 A CN 201811619632A CN 109503427 B CN109503427 B CN 109503427B
- Authority
- CN
- China
- Prior art keywords
- mmol
- phenylanthracene
- substituted
- electron
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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
[ 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＝ηeh·ηPL·ηexciton·ηout1 × 0.08 × 0.25 × 0.3 ═ 0.6% ], wherein ηehIs the recombination rate of electrons and holes; etaPLFluorescence quantum yield eta for clean membranesexcitonThe ratio of excitons; etaoutIs 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:
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).
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).
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
Example 2
Example 3
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 (7)
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);
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.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811619632.0A CN109503427B (en) | 2018-12-28 | 2018-12-28 | D-A type organic blue fluorescent material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811619632.0A CN109503427B (en) | 2018-12-28 | 2018-12-28 | D-A type organic blue fluorescent material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109503427A CN109503427A (en) | 2019-03-22 |
| CN109503427B true CN109503427B (en) | 2021-10-08 |
Family
ID=65755595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811619632.0A Active CN109503427B (en) | 2018-12-28 | 2018-12-28 | D-A type organic blue fluorescent material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109503427B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761879B (en) * | 2019-01-10 | 2022-03-29 | 太原理工大学 | Organic blue fluorescent material, preparation method thereof and organic electroluminescent device |
| CN110041179A (en) * | 2019-04-24 | 2019-07-23 | 上海大学 | 9,10- bis- (2,4- dimethoxy-biphenyl base) anthracene, its ring tripolymer compound and its preparation method and application |
| CN111521601B (en) * | 2020-04-22 | 2022-01-25 | 中国科学院宁波材料技术与工程研究所 | Application of ratio-type fluorescent polymer hydrogel in seafood freshness detection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1576265A (en) * | 2003-06-27 | 2005-02-09 | 佳能株式会社 | Substituted anthryl derivative and electroluminescence device using the same |
| CN101426760A (en) * | 2006-04-21 | 2009-05-06 | Lg化学株式会社 | Novel anthracene derivatives, method for preparation thereof, and organic electronic device using the same |
| CN108383693A (en) * | 2018-02-06 | 2018-08-10 | 陕西师范大学 | A kind of organic blue fluorescent material and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6187080B2 (en) * | 2012-10-11 | 2017-08-30 | Tdk株式会社 | Electroluminescent device |
-
2018
- 2018-12-28 CN CN201811619632.0A patent/CN109503427B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1576265A (en) * | 2003-06-27 | 2005-02-09 | 佳能株式会社 | Substituted anthryl derivative and electroluminescence device using the same |
| CN101426760A (en) * | 2006-04-21 | 2009-05-06 | Lg化学株式会社 | Novel anthracene derivatives, method for preparation thereof, and organic electronic device using the same |
| CN108383693A (en) * | 2018-02-06 | 2018-08-10 | 陕西师范大学 | A kind of organic blue fluorescent material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Organic light-Emitting diode based on bis(10-phenylanthracen-9-yl)benzene derivatives with a stable white emission;Young Seok Kim 等;《Journal of Photochemistry and Photobiology, A:Chemistry》;20150528;第310卷;第135页右栏倒数第1段，第135页2.1和图解1和第134页的摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109503427A (en) | 2019-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110627822A (en) | Green light narrow spectrum three-coordination boron luminescent compound, luminescent composition and application thereof | |
| KR20100028154A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| CN112979709B (en) | Metal complex and application thereof | |
| CN105820190B (en) | Application of the feux rouges to near-infrared phosphorescent iridium complex luminescent material and its in electroluminescent device | |
| CN109503427B (en) | D-A type organic blue fluorescent material and preparation method and application thereof | |
| CN111943961B (en) | Organic electroluminescent compound based on phenazine-thiophene-dicyano and application | |
| CN108383693A (en) | A kind of organic blue fluorescent material and its preparation method and application | |
| CN109265310A (en) | A kind of organic blue fluorescent material and its preparation method and application | |
| CN115304566A (en) | Luminescent auxiliary material and preparation method and application thereof | |
| CN115197184A (en) | Luminescent auxiliary material and preparation method and application thereof | |
| CN114605412A (en) | White light electroluminescent device doped with dipyridyl phenazine thermal activation delayed fluorescent material | |
| CN108997201A (en) | A kind of miscellaneous anthracene compound of spiro fluorene and its organic electroluminescence device | |
| CN106632231B (en) | A kind of Hete rocyclic derivatives and the organic luminescent device using the Hete rocyclic derivatives | |
| CN110577488A (en) | Compound with carbazole as core and application thereof in organic electroluminescent device | |
| CN111454251A (en) | Pyrazine derivative and application thereof in O L ED device | |
| CN110294735B (en) | Compound with anthracene and phenanthrene as core and application of compound in organic electroluminescent device | |
| CN114644632A (en) | Thermal activation delayed fluorescence material based on bispyridophenazine receptor and preparation method and application thereof | |
| CN110845508A (en) | Compound with spirofluorene anthrone as core, preparation method and application thereof | |
| CN111320615B (en) | Small molecules based on S, S-dioxo-dibenzothiophene and phenanthroimidazole and application thereof in electroluminescent device | |
| CN112159326A (en) | Compound, luminescent layer dye material and organic electroluminescent device | |
| CN110615783A (en) | Electroluminescent material with pyrazinoindenone as electron acceptor and application thereof | |
| CN113896724B (en) | Organic red light micromolecule based on benzothiadiazole-pyrene imidazole and application thereof in preparation of undoped organic electroluminescent device | |
| CN113896719A (en) | Pure organic fluorescent micromolecules with high exciton utilization rate and application thereof | |
| CN109608403B (en) | Anthracene-tetraphenylethylene-based organic blue light small molecule and application thereof in preparation of non-doped organic electroluminescent device | |
| CN110343049B (en) | Organic compound with spiro dibenzosuberene fluorene as skeleton and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |