CN109232376A - A kind of fluorene derivative and its organic electroluminescence device - Google Patents

A kind of fluorene derivative and its organic electroluminescence device Download PDF

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CN109232376A
CN109232376A CN201811118218.1A CN201811118218A CN109232376A CN 109232376 A CN109232376 A CN 109232376A CN 201811118218 A CN201811118218 A CN 201811118218A CN 109232376 A CN109232376 A CN 109232376A
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unsubstituted
substituted
fluorene derivative
layer
cyano
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董秀芹
蔡辉
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Changchun Haipurunsi Technology Co Ltd
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Changchun Haipurunsi Technology Co Ltd
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Abstract

The present invention provides a kind of fluorene derivative and its organic electroluminescence device, is related to organic optoelectronic materials technology.The present invention connects strong electron-withdrawing group group by double bond in fluorenes main structure, one or both sides connect substituted or unsubstituted 4H- benzo carbazole structure and form a kind of fluorene derivative, it is with good electron transport ability and cavity transmission ability, the injection rate of carrier and exciton recombination rate in luminescent layer can be effectively improved, and thermal stability is good, good film-forming property, it synthesizes simple to operation, it can be applied in organic luminescent device as layer main body and/or the hole blocking layer of shining, it is uneven that carrier transport in organic luminescent device can effectively be solved, luminous efficiency is low, service life is short, photochromic unstable problem, its organic luminescent device has driving voltage low, luminous efficiency is high, the advantage of service life length.

Description

A kind of fluorene derivative and its organic electroluminescence device
Technical field
The present invention relates to organic photoelectrical material technical field more particularly to a kind of fluorene derivatives and its organic electroluminescence Part.
Background technique
There is Pope et al. to issue faint this organic electroluminescence of blue light as luminescent layer using single layer anthracene crystal from 1963 to send out After optical phenomenon, 1987, double-layer structure device was made using vacuum evaporation mode in Deng Qingyun of Kodak et al., Under voltage less than 10V, device exterior quantum efficiency reaches 1%, this behave has electroluminescent organic material and device There is the possibility of practicability, to drive organic material in the research boom in this electroluminescent field, by nearly 30 years hairs Exhibition, organic electroluminescence device efficiency have obtained biggish promotion, and because its with self-luminous, visual angle is wide, all solidstate, full-color Change, reaction speed is fast, high brightness, low driving voltage, thickness is thin, light weight, can make the features such as large scale and curved panel, has Organic electroluminescence devices have obtained more and more applications in monitor market, become current most potential Display panel skill Art.
The principle of organic electroluminescent: apply external voltage at cathode and an anode both ends, injected respectively at cathode and anode The carriers such as electronics and hole, hole and electronics pass through the interface of hole transmission layer and electron transfer layer respectively, are finally shining Layer is compounded to form exciton, and exciton is excitation state, unstable, and energy returns to stable base for releasing in the form of light or heat State, when appearance is organic electroluminescent in the form of light.
Classical its structure of organic electroluminescence device is sandwich structure, generally comprises cathode, anode and in the two Between organic matter layer.Its organic matter layer substantially may include hole injection layer, hole transmission layer, shine auxiliary layer, luminescent layer, sky One of cave barrier layer, electron transfer layer, electron injecting layer are a variety of, wherein electron injecting layer, electron transfer layer, hole resistance Barrier, shine auxiliary layer, hole injection layer and hole transmission layer, and effect is mainly equilbrium carrier injection so that electronics with Hole effectively combines in luminescent layer and forms exciton, and then shines, and improves luminous efficiency.Luminescent layer generally comprises material of main part and visitor Body dopant material is primarily used to realize the compound of electrons and holes, shine to realize.
All in all, the direction of the following organic electroluminescence device is to develop high efficiency, high brightness, long-life, low cost White light parts and full color display device, but the technological industrialization process still faces many critical issues, wherein due to big In most transmission materials, the transmission performance in hole is better than electronics, causes the amount in hole in luminescent layer to be more than the amount of electronics, to lead Cause the recombination probability of exciton low, the transmission performance of electronics limits the promotion of the efficiency of organic electroluminescence device.Further, since Hole amount is more than electronics in luminescent layer, and hole will continue to transmit to cathode side, cause the offset of light emitting region, cause device photochromic Unstable, local energy accumulation, material degradation aggravation, the efficiency roll-off for eventually leading to device is serious, and the lost of life is serious.Therefore Carrier injection balance how is adjusted, device light emitting efficiency, service life and photochromic stability is improved and is asked as urgently to be resolved Topic.
Summary of the invention
The object of the present invention is to provide a kind of fluorene derivative and its organic electroluminescence device, fluorenes provided by the invention is derivative Object has good electronics and cavity transmission ability, and electron transport ability is better than cavity transmission ability, and the biography of electronics can be improved Defeated performance balances the injection of carrier and recombination probability in luminescent layer, and thermal stability is good, good film-forming property, and synthetic method is simply easy Operation using organic electroluminescence device prepared by the fluorene derivative there is good luminous efficiency and service life to show.
The present invention provides a kind of fluorene derivatives, and general formula of molecular structure is as shown in chemical formula I:
Wherein, any one of A in following group:
R1、R2Independently selected from cyano, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 is miscellaneous Any one in aryl, any one or a few in halogen atom, cyano, trifluoromethyl of the substituent group；L is selected from Singly-bound, substituted or unsubstituted C6~C30 aryl, any one in substituted or unsubstituted C3~C30 heteroaryl；R3It is selected from H, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl replace Or any one in unsubstituted C3~C60 heteroaryl；R4、R5Independently selected from H, halogen, cyano, trifluoromethyl, substitution or Unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, in substituted or unsubstituted C3~C30 heteroaryl Any one；R6Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, replaces or do not take Any one in C3~C30 heteroaryl in generation.
Preferably, any one of L in singly-bound or group as follows:
Wherein, X is selected from CR7R8、O、S、NR9In any one；R7、R8Independently selected from H, substituted or unsubstituted C1~ C10 alkyl, substituted or unsubstituted C6~C18 aryl, any one in substituted or unsubstituted C3~C18 heteroaryl, R7、 R8It is not simultaneously H, R7、R8Cyclization can be connected；R9Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~ Any one in C18 aryl, substituted or unsubstituted C3~C18 heteroaryl.
Preferably, R3、R4、R5Independently selected from H, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, Sec-butyl, substituted or unsubstituted following group: phenyl, naphthalene, anthryl, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, Thienyl, benzofuranyl, benzothienyl, dibenzofuran group, dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, It is quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, quinazolyl, indyl, any one in azepine carbazyl Kind；R6Selected from methyl, ethyl, isopropyl, tert-butyl, sec-butyl, substituted or unsubstituted following group: phenyl, naphthalene, anthracene Base, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuran group, Dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, quinoline azoles Quinoline base, indyl, any one in azepine carbazyl.
Preferably, R1、R2Any one in cyano or following group:
Wherein X1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11、X12、X13Independently selected from halogen, cyano, trifluoromethyl In any one.
Further preferably, R1、R2Independently selected from any one in cyano or following group:
Further preferably, R1、R2At least one is selected from cyano.
Most preferably, any one of fluorene derivative of the present invention in chemical structure as follows:
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes cathode, anode And the one or more organic matter layers being placed between two electrode, it is derivative that the organic matter layer contains fluorenes of the present invention Object.
Preferably, organic matter layer described in organic matter layer of the present invention includes luminescent layer, and luminescent layer includes main body and doping Object, shine layer main body in contain any fluorene derivative of the present invention.
Preferably, organic matter layer of the present invention includes hole blocking layer, is contained in hole blocking layer of the present invention Any fluorene derivative.
Beneficial effects of the present invention:
The present invention provides a kind of fluorene derivative and its organic electroluminescence device.The present invention is in fluorenes main structure by double It is keyed strong electron-withdrawing group group, one or both sides connect substituted or unsubstituted 4H- benzo carbazole structure, to obtain the present invention The fluorene derivative.
Fluorenes main structure triplet with higher itself, has both hole and electron transport ability, passes through at its 9 Double bond connects strong electron-withdrawing group group, modifies its structure, makes it have stronger electron-withdrawing ability, on this basis directly Connection is connected by conjugated structure with 4H- benzo carbazole structure, and biggish conjugated system is formed, and has both hole and electronics passes Movement Capabilities, and electron transport ability is enhanced, conducive to the transmission of electrons and holes and compound.
Fluorene derivative of the present invention has biggish conjugated system, and structural rigidity is big, disperses charge more, improves The stability of material；And its molecular weight increases, and both improves glass transition temperature, makes it be not easy to crystallize, and reduce molecule Coplanarity is easy to form a film.
Fluorene derivative of the present invention has good electron transport ability and corresponding cavity transmission ability, can apply It is used as luminescent layer bipolar host material and/or hole blocking layer in organic electroluminescence device, luminescent layer can be effectively improved The injection rate and reduction loss amount of the hole to cathode side of middle electronics are reduced to improve the luminous efficiency of device due to sky Energy accumulation caused by cave is transmitted to cathode side, and then improve the service life and photochromic stability of device.Using institute of the present invention There is the organic electroluminescence device for stating fluorene derivative preparation good luminous efficiency and service life to show.
Fluorene derivative preparation method of the present invention is simple, and raw material is easy to get, and can satisfy industrialization demand.
Specific embodiment:
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, art technology Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
Aryl of the present invention refers to remove a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule after, be left the total of univalent perssad Claiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but It is without being limited thereto.
Heteroaryl of the present invention be the heteroaromatic being made of carbon and hetero atom core carbon on remove a hydrogen atom, be left The general name of univalent perssad, the hetero atom include but is not limited to oxygen, sulphur, nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl Or fused ring heteroaryl, embodiment may include carbazyl, acridinyl, benzothienyl, benzofuranyl, dibenzofuran group, two Benzothienyl, carbazyl etc., but not limited to this.
The present invention provides a kind of fluorene derivatives, and general formula of molecular structure is as shown in chemical formula I:
Wherein, any one of A in following group:
R1、R2Independently selected from cyano, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 is miscellaneous Any one in aryl, any one or a few in halogen atom, cyano, trifluoromethyl of the substituent group；L is selected from Singly-bound, substituted or unsubstituted C6~C30 aryl, any one in substituted or unsubstituted C3~C30 heteroaryl；R3It is selected from H, halogen, cyano, trifluoromethyl, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl replace Or any one in unsubstituted C3~C60 heteroaryl；R4、R5Independently selected from H, halogen, cyano, trifluoromethyl, substitution or Unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, in substituted or unsubstituted C3~C30 heteroaryl Any one；R6Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, replaces or do not take Any one in C3~C30 heteroaryl in generation.
According to the present invention, the substituted alkyl, substituted aryl, substituted heteroaryl, wherein the substituent group is independent Ground is selected from deuterium, cyano, halogen, trifluoromethyl, C1-C10Alkyl, C6-C24Aryl or C3-C24Heteroaryl, preferably F atom, Cl are former Son, cyano, trifluoromethyl, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, naphthalene, pyridyl group, pyrimidine radicals, triazine radical In any one.
Preferably, any one of L in singly-bound or group as follows:
Wherein, X is selected from CR7R8、O、S、NR9In any one；R7、R8Independently selected from H, substituted or unsubstituted C1~ C10 alkyl, substituted or unsubstituted C6~C18 aryl, any one in substituted or unsubstituted C3~C18 heteroaryl, R7、 R8It is not simultaneously H, R7、R8Cyclization can be connected；R9Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~ Any one in C18 aryl, substituted or unsubstituted C3~C18 heteroaryl.
Preferably, R3、R4、R5Independently selected from H, halogen, cyano, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, Sec-butyl, substituted or unsubstituted following group: phenyl, naphthalene, anthryl, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, Thienyl, benzofuranyl, benzothienyl, dibenzofuran group, dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, It is quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, quinazolyl, indyl, any one in azepine carbazyl Kind；R6Selected from methyl, ethyl, isopropyl, tert-butyl, sec-butyl, substituted or unsubstituted following group: phenyl, naphthalene, anthracene Base, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuran group, Dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, quinoline azoles Quinoline base, indyl, any one in azepine carbazyl.
Preferably, R1、R2Any one in cyano or following group:
Wherein X1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11、X12、X13Independently selected from halogen, cyano, trifluoromethyl In any one.
Further preferably, R1、R2Independently selected from any one in cyano or following group:
Further preferably, R1、R2At least one is selected from cyano.
Most preferably, as an example, it is not particularly limited, a kind of fluorene derivative of the present invention is selected from chemistry as follows Any one in structure:
Fluorene derivative of the present invention is obtained by following synthetic route:
Fluorene derivative of the present invention obtains as follows:
1, raw material a-1, R6-B(OH)2, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, is reacted in obtaining Mesosome 1-1；Intermediate 1-1, R4-B(OH)2, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains intermediate 1-2；In Mesosome 1-2, isopropanol pinacol borate, using n-BuLi as alkali, reaction obtains intermediate 1-3；Intermediate 1-3, raw material I- L-Br, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains intermediate 1-4；Intermediate 1-4, isopropanol pinacol boron Acid esters, using n-BuLi as alkali, reaction obtains intermediate 1-5；
2, raw material -2, R4-B(OH)2、R5-B(OH)2, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains centre Body 2-1；Intermediate 2-1, raw material I-L-Br, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains intermediate 2-2；In Mesosome 2-2, isopropanol pinacol borate, using n-BuLi as alkali, reaction obtains intermediate 2-3；
3, by solvent, potassium carbonate of DMF it is raw material a-3, a-4, alkali, obtains intermediate b-1；
4, acetic acid is added in intermediate b-1, sulfuric acid reaction obtains intermediate b-2；
5, raw material a-5, malononitrile, using DMF as solvent, reaction obtains intermediate b-3-1；Raw material a-5, intermediate b-2, second Potassium alcoholate is dissolved in ethanol solution reaction and obtains intermediate b-3-2；
6, intermediate b-3-1 or b-3-2, raw material a-6, with Pd (PPh3)4For catalyst, K2CO3For alkali, react in obtaining Mesosome b-4；
7, intermediate b-4,1-5, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains chemical compounds I -1；Intermediate B-4,2-3, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, and reaction obtains chemical compounds I -2.
The present invention limitation not special to above-mentioned reaction be using popular response well-known to those skilled in the art Can, the preparation method is simple, easily operated.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes cathode, anode And the one or more organic matter layers being placed between two electrode, it is derivative that the organic matter layer contains fluorenes of the present invention Object.
Organic matter layer of the present invention is selected from hole injection layer, hole transmission layer, luminescent layer, and (light emitting host adulterates object Form or single substance form are as luminescent layer), hole blocking layer, electron transfer layer, at least one of electron injecting layer.
Preferably, the organic matter layer luminescent layer, luminescent layer include main body and doping object, contain this in the layer main body that shines Invention any fluorene derivative.
Luminous layer main body can be the single substance for only containing fluorene derivative of the present invention, can also be of the present invention The mixture of the mixture of fluorene derivative or fluorene derivative of the present invention and other compounds.
Preferably, the organic matter layer includes hole blocking layer, is contained in hole blocking layer of the present invention any Fluorene derivative.
Its structure of organic electroluminescence device of the present invention is preferred are as follows: substrate/anode/hole injection layer/hole passes Defeated layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/cathode.However, the structure of organic electroluminescence device It is without being limited thereto.Organic electroluminescence device of the present invention can be carried out according to the characteristic of device parameter requirements and material selection and Combination, can also add or omit part organic layer.
Organic electroluminescence device structure of the present invention is further preferably are as follows: ITO is as transparent anode；2-TNATA conduct Hole injection layer；NPB is as hole transmission layer；CBP, fluorene derivative of the invention, the mixture of fluorene derivative of the present invention or sheet Invent mixture/Ir (ppy) of the fluorene derivative Yu other compounds3As luminescent layer substance；Fluorene derivative of the invention As hole blocking layer；Alq3As electron transfer layer；LiF is used as electron injecting layer；Al is used as cathode.
Fluorene derivative of the present invention is used as the layer main body that shines, and the organic electroluminescence to manufacture construction same as below is sent out Optical device:
The mixture or fluorenes of the present invention of ITO/2-TNATA/NPB/ fluorene derivative of the present invention, fluorene derivative of the present invention The mixture of derivative and other compounds: Ir (ppy)3/BAlq/Alq3/LiF/Al。
Fluorene derivative of the present invention is used as hole blocking layer, and the organic electroluminescence to manufacture construction same as below is sent out Optical device:
ITO/2-TNATA/NPB/CBP:Ir (ppy)3/ fluorene derivative/Alq of the present invention3/LiF/Al。
Fluorene derivative of the present invention is used as hole barrier materials and luminous layer main body, to have manufactured structure same as below The organic electroluminescence device made:
The mixture or fluorenes of the present invention of ITO/2-TNATA/NPB/ fluorene derivative of the present invention, fluorene derivative of the present invention The mixture of derivative and other compounds: Ir (ppy)3/ fluorene derivative/Alq of the present invention3/LiF/Al。
Organic electroluminescence device of the present invention can be widely applied to Display panel, lighting source, flexibility OLED, electronics The fields such as paper, Organophotoreceptor or Organic Thin Film Transistors, direction board, signal lamp.
The synthesis of [embodiment 1] compound A-1
Step1: under nitrogen environment, in reactor be added raw material a-1 (1.93g, 10mmol), iodobenzene (2.5g, 12mmol), 1,10- phenanthroline (0.2g, 1.0mmol), CuI (0.2g, 2.0mmol), K2CO3(4.1g, 30mmol), 30mL's DMF is stirred to react for 24 hours under the conditions of 80 DEG C, after be cooled to room temperature, three times with deionized water and diethyl ether partial extraction, will have Machine is mutually collected and utilizes anhydrous MgSO4It is dried and evaporated solvent, residue crosses silica gel column chromatography and purifies to obtain intermediate A -1-1 (2.39g, 89%).
Step2: under nitrogen environment, intermediate A -1-1 (10.0g, 37.1mmol), 100mL dichloromethane are added in reactor Alkane, point 5 equivalent are intermittently added iodine (3.58g, 14.1mmol), KIO afterwards3(2.38g, 11.13mmol), after be stirred to react 6h, It is washed afterwards with methanol, obtains intermediate A -1-2 (8.50g, 58%).
Step3: under oxygen environment, intermediate A -1-2 (10g, 25.3mmol), 100mL toluene, DDQ are added in reactor (1.57g, 7.6mmol), NaNO2(0.52g, 7.6mmol) reacts 6h under the conditions of 110 DEG C, is cooled to room temperature after reaction, Evaporation of solvent, residue cross silica gel column chromatography and purify to obtain intermediate A -1-3 (8.94g, 90%).
Step4: under nitrogen environment, being added the THF of intermediate A -1-3 (10g, 25.3mmol), 30mL in reactor, - 78 DEG C of n-BuLi for being slowly dropped into 10mL (hexane solution of 25.0mmol, 2.5M) are stirred to react 1h at -78 DEG C, and slowly It is added dropwise isopropanol pinacol borate (9.3mL, 50mmol), continues to be stirred to react 1h, reaction is then stirred at room temperature for 24 hours, The 10%HCl aqueous solution of 5mL and the H of 50mL are added after the reaction was completed2Then O extracts reaction with the diethyl ether moiety of 80mL Mixture three times, organic phase is collected and utilizes anhydrous MgSO4It is dried and evaporated solvent, residue is crossed during silica gel column chromatography obtains Mesosome A-1-4 (7.49g, 75%).
Step5: under nitrogen protection, it is completely molten that the bromo- 9-Fluorenone of compound 2- (2.59g, 10mmol) is added into reactor Solution stirs under room temperature in 50mL DMF solution, and malononitrile (0.79g, 12mmol) is added afterwards, is stirred to react 1h under room temperature, instead Deionized water is added after answering and stops reaction, stirs 10min, sediment is obtained by filtration, sediment is diluted with ethyl acetate, Anhydrous MgSO4It dries, filters, be concentrated, cross silica gel column chromatography and obtain intermediate A -1-5 (1.66g, 54%).
Step6: under condition of nitrogen gas, intermediate A -1-5 (3.07g, 10mmol), intermediate A -1-4 are added into reactor (3.93g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, second Alcohol 20mL and distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in filtering In ethyl acetate, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, being recrystallized to give It closes object A-1 (3.95g, 80%).
The synthesis of [embodiment 2] compound A-3
Step1: phenyl-pentafluoride nitrile (1.93g, 10mmol), ethyl cyanoacetate (1.11g, 10mmol), carbon are added in reactor Sour potassium (1.67g, 12.1mmol), 30mL DMF, be stirred to react 48h at room temperature, it is rear distilled water to be added and acetic acid terminates reaction, It is extracted with dichloromethane and is concentrated to get intermediate A -3-1 (2.83g, 99%).
Step2: intermediate A -3-1 (2.86g, 10mmol), 50% acetic acid (4.10mL) and sulfuric acid are added in reactor (0.2mL), flow back 16h after stir, be cooled to room temperature in mixture, be added dropwise 10mL cold distilled water terminate reaction, stir 0.5h afterwards, Reaction mixture distilled water and chloroform are extracted, intermediate A -3-2 (2.08g, 97%) is then concentrated to get.
Step3: under nitrogen protection, the bromo- 9-Fluorenone of 2- (2.59g, 10mmol), intermediate A -3-2 are added in reactor (2.57g, 12mmol) and sodium ethoxide (2.04g, 30mmol) are dissolved completely in 30ml ethyl alcohol, then heat and stir gained it is molten Liquid.After reaction terminates, dilute the residue that obtains and being concentrated under reduced pressure products therefrom with tetrahydrofuran, and with water with Salt water washing.Organic solvent layer is collected, removes moisture through anhydrous magnesium sulfate, then filtration residue is concentrated under reduced pressure.Concentration Solution obtain intermediate A -3-3 (2.49g, 56%) with silica gel chromatography.
Step4: under condition of nitrogen gas, intermediate A -3-3 (4.55g, 10mmol), intermediate A -1-4 are added into reactor (3.93g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, second Alcohol 20mL and distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in filtering In ethyl acetate, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, being recrystallized to give It closes object A-3 (5.13g, 80%).
The synthesis of [embodiment 3] compound A-32
Step1: under condition of nitrogen gas, into reactor be added raw material a-2 (3.49g, 10mmol), phenyl boric acid (2.44g, 20mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, ethyl alcohol 20mL and Distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in acetic acid second by filtering In ester, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, is recrystallized to give intermediate A- 32-1 (2.75g, 80%).
Step2: intermediate A -32-2 is obtained according to the synthetic method of 2 intermediate A -3-1 of embodiment.
Step3: intermediate A -32-3 is obtained according to the synthetic method of 2 intermediate A -3-2 of embodiment.
Step4: intermediate A -32-4 is obtained according to the synthetic method of 2 intermediate A -3-3 of embodiment.
Step5: intermediate A -32-4 (3.59g, 8mmol), A-32-1 (2.75g, 8mmol), Pd are added in reactor2 (dba)3(0.17g, 0.2mmol), P (t-Bu)3(0.14,0.67mmol), NaOt-Bu (2.24g, 20mmol), toluene solution 100mL reacts for 24 hours under the conditions of 100 DEG C, extracts organic phase, organic layer MgSO with ether and water after reaction4It is dry, it is dense Contracting organic matter crosses column chromatography, is recrystallized to give compound A-32 (4.43g, 78%).
The synthesis of [embodiment 4] compound A-107
Step1: under nitrogen environment, in reactor be added raw material a-2 (2.79g, 8mmol), iodobenzene (1.63g, 8mmol), Pd2(dba)3(0.17g, 0.2mmol), P (t-Bu)3(0.14,0.67mmol), NaOt-Bu (2.24g, 20mmol), toluene are molten Liquid 100mL reacts for 24 hours under the conditions of 100 DEG C, extracts organic phase, organic layer MgSO with ether and water after reaction4It is dry, Condensed organic crosses column chromatography, is recrystallized to give compound A-107-1 (2.72g, 80%).
Step2: under condition of nitrogen gas, intermediate A -107-1 (4.25g, 10mmol), 5- pyrimidine boronic acid are added into reactor (1.24g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, second Alcohol 20mL and distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in filtering In ethyl acetate, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, being recrystallized to give It closes object A-107-2 (3.35g, 79%).
Step3: under nitrogen environment, intermediate A -107-2 (10.73g, 25.3mmol), 30mL are added in reactor THF is slowly dropped into the n-BuLi of 10mL (hexane solution of 25.0mmol, 2.5M) at -78 DEG C, is stirred to react 1h at -78 DEG C, And isopropanol pinacol borate (9.3mL, 50mmol) is slowly added dropwise, continue to be stirred to react 1h, then be stirred at room temperature anti- The 10%HCl aqueous solution of 5mL and the H of 50mL should for 24 hours, be added after the reaction was completed2Then O is extracted with the diethyl ether moiety of 80mL It takes reaction mixture three times, organic phase is collected and utilizes anhydrous MgSO4It is dried and evaporated solvent, residue crosses silica gel column chromatography Obtain intermediate A -107-3 (8.71g, 73%).
Step4: under condition of nitrogen gas, intermediate A -32-4 (4.47g, 10mmol), A-107-3 are added into reactor (4.71g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, second Alcohol 20mL and distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in filtering In ethyl acetate, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, being recrystallized to give It closes object A-107 (5.56g, 78%).
The synthesis of [embodiment 5] compound A-153
Step1: under nitrogen protection, 2,7-, bis- bromo- 9-Fluorenone (3.38g, 10mmol), intermediate A -3- are added in reactor 2 (2.57g, 12mmol) and sodium ethoxide (2.04g, 30mmol) are dissolved completely in 30ml ethyl alcohol, are then heated and are stirred gained Solution.After reaction terminates, the residue obtained and being concentrated under reduced pressure products therefrom is diluted with tetrahydrofuran, and use water With salt water washing.Organic solvent layer is collected, removes moisture through anhydrous magnesium sulfate, then filtration residue is concentrated under reduced pressure.It is dense The solution of contracting obtains intermediate A -153-1 (2.99g, 56%) with silica gel chromatography.
Step2: under condition of nitrogen gas, intermediate A -153-1 (5.34g, 10mmol), intermediate A -1- are added into reactor 4 (7.87g, 20mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, second Alcohol 20mL and distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in filtering In ethyl acetate, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, being recrystallized to give It closes object A-153 (6.35g, 70%).
The synthesis of [embodiment 6] compound B-2
Compound B-2 (4.33g, 79%) is obtained according to the synthetic method of 2 compound A-3 of embodiment
The synthesis of [embodiment 7] compound B-55
Step1: under condition of nitrogen gas, into reactor be added to bromo-iodobenzene (2.83g, 10mmol), A-1-4 (3.93g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, ethyl alcohol 20mL and Distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in acetic acid second by filtering In ester, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, is recrystallized to give compound B- 55-1 (3.38g, 80%).
Step2: under nitrogen environment, being added the THF of intermediate B -55-1 (10.68g, 25.3mmol), 30mL in reactor, It is slowly dropped into the n-BuLi of 10mL (hexane solution of 25.0mmol, 2.5M) at -78 DEG C, 1h is stirred to react at -78 DEG C, and delay It is slow that isopropanol pinacol borate (9.3mL, 50mmol) is added dropwise, continue to be stirred to react 1h, reaction is then stirred at room temperature For 24 hours, the 10%HCl aqueous solution of 5mL and the H of 50mL are added after the reaction was completed2Then O is extracted with the diethyl ether moiety of 80mL Reaction mixture three times, organic phase is collected and utilizes anhydrous MgSO4It is dried and evaporated solvent, residue is crossed silica gel column chromatography and obtained To intermediate B -55-2 (8.79g, 74%).
Step3: compound B-55-3 is obtained according to the synthetic method of 2 intermediate A -3-1 of embodiment.
Step4: compound B-55-4 is obtained according to the synthetic method of 2 intermediate A -3-2 of embodiment.
Step5: compound B-55-5 is obtained according to the synthetic method of 2 intermediate A -3-3 of embodiment.
Step6: compound B-55 (5.41g, 78%) is obtained according to the synthetic method of the Step4 of compound A-3.
The synthesis of [embodiment 8] compound B-94
Step1: compound B-94-1 is obtained according to the synthetic method of 2 intermediate A -3-2 of embodiment.
Step2: under nitrogen protection, 2,7-, bis- bromo- 9-Fluorenone (3.38g, 10mmol), intermediate B-are added in reactor 94-1 (2.08g, 12mmol) and sodium ethoxide (2.04g, 30mmol) are dissolved completely in 30ml ethyl alcohol, are then heated and are stirred institute Obtain solution.After reaction terminates, the residue obtained and being concentrated under reduced pressure products therefrom is diluted with tetrahydrofuran, is used in combination Water and salt water washing.Organic solvent layer is collected, removes moisture through anhydrous magnesium sulfate, then filtration residue is concentrated under reduced pressure. The solution of concentration obtains intermediate B -94-2 (2.76g, 56%) with silica gel chromatography.
Step3: under nitrogen environment, in reactor be added raw material a-3 (1.53g, 8mmol), B-94-2 (7.89g, 16mmol)、Pd2(dba)3(0.17g, 0.2mmol), P (t-Bu)3(0.14,0.67mmol), NaOt-Bu (2.24g, 20mmol), toluene solution 100mL reacts for 24 hours under the conditions of 100 DEG C, extracts organic phase with ether and water after reaction, organic Layer uses MgSO4Dry, condensed organic crosses column chromatography, is recrystallized to give compound B-94 (4.28g, 75%).
The synthesis of [embodiment 9] compound B-109
Step1: the bromo- 7- iodine Fluorenone (3.85g, 10mmol) of 2-, intermediate B -55-4 are added under nitrogen protection, in reactor (2.57g, 12mmol) and sodium ethoxide (2.04g, 30mmol) are dissolved completely in 30ml ethyl alcohol, then heat and stir gained it is molten Liquid.After reaction terminates, dilute the residue that obtains and being concentrated under reduced pressure products therefrom with tetrahydrofuran, and with water with Salt water washing.Organic solvent layer is collected, removes moisture through anhydrous magnesium sulfate, then filtration residue is concentrated under reduced pressure.Concentration Solution obtain intermediate B -109-1 (3.25g, 56%) with silica gel chromatography.
Step2: under condition of nitrogen gas, intermediate B -109-1 (5.81g, 10mmol), phenyl boric acid are added into reactor (1.22g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, second Alcohol 20mL and distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in filtering In ethyl acetate, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, being recrystallized to give It closes object B-109-2 (3.96g, 78%).
Step3: under condition of nitrogen gas, intermediate B -109-2 (5.07g, 10mmol), A-1-4 are added into reactor (3.93g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene 100mL, second Alcohol 20mL and distilled water 20mL is stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filter cake is dissolved in filtering In ethyl acetate, diatomite is crossed, extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, being recrystallized to give It closes object B-109 (5.41g, 78%).
The fluorene derivative FD-MS value of synthesis of the embodiment of the present invention is as shown in table 1.
[table 1]
[comparative example 1] device prepares embodiment:
Ito glass substrate is placed in distilled water and is cleaned 2 times, it is ultrasonic washing 30 minutes, different after distilled water cleans Ultrasonic washing is later dry in order for propyl alcohol, acetone, methanol equal solvent, is transferred in plasma washing machine, by above-mentioned base Plate washs 5 minutes, is sent in evaporator.
Hole injection layer 2-TNATA/60nm, hole transmission layer are successively deposited on the ito transparent electrode having had been prepared for Compound N PB/60nm, vapor deposition main body CBP: doping Ir (ppy)310% mixing/30nm, hole blocking layer BAlq/10nm, electricity Sub- transport layer Alq3/ 30nm, electron injecting layer LiF/0.2nm, cathode Al/150nm.
[embodiment 10] device prepares embodiment:
The compound BAlq of the hole blocking layer of comparative example 1 is changed to the compound A-1 of embodiment 1.
[embodiment 11] device prepares embodiment:
The compound BAlq of the hole blocking layer of comparative example 1 is changed to the compound A-3 of embodiment 2.
[embodiment 12] device prepares embodiment:
The compound BAlq of the hole blocking layer of comparative example 1 is changed to the compound A-32 of embodiment 3.
[embodiment 13] device prepares embodiment:
The compound BAlq of the hole blocking layer of comparative example 1 is changed to the compound A-107 of embodiment 4.
[embodiment 14] device prepares embodiment:
The compound BAlq of the hole blocking layer of comparative example 1 is changed to the compound A-153 of embodiment 5.
[embodiment 15] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-2 of embodiment 6.
[embodiment 16] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-55 of embodiment 7.
[embodiment 17] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-94 of embodiment 8.
[embodiment 18] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-109 of embodiment 9.
[embodiment 19] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-2 of embodiment 6, hole barrier The compound BAlq of layer is changed to the compound A-3 of embodiment 2.
[embodiment 20] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-55 of embodiment 7, hole resistance The compound BAlq of barrier is changed to the compound A-32 of embodiment 3.
[embodiment 21] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-94 of embodiment 8, hole resistance The compound BAlq of barrier is changed to the compound A-107 of embodiment 4.
[embodiment 22] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound B-109 of embodiment 9, hole resistance The compound BAlq of barrier is changed to the compound A-153 of embodiment 5.
[embodiment 23] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound A-107 of embodiment 4, hole resistance The compound BAlq of barrier is changed to the compound A-3 of embodiment 2.
[embodiment 24] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to the compound A-107 of embodiment 4, hole resistance The compound BAlq of barrier is changed to the compound A-32 of embodiment 3.
[embodiment 25] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to A-3:B-2 (40%:50%).
[embodiment 26] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to A-3:B-55 (40%:50%).
[embodiment 27] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to A-3:B-2 (40%:50%), hole barrier The compound BAlq of layer is changed to the compound A-1 of embodiment 1.
[embodiment 28] device prepares embodiment:
The compound CBP of the luminous layer main body of comparative example 1 is changed to A-3:B-55 (40%:50%), hole resistance The compound BAlq of barrier is changed to the compound A-32 of embodiment 3.
The characteristics of luminescence test result such as table 2 of luminescent device prepared by 10-28 of the embodiment of the present invention and comparative example 1 It is shown:
[table 2]
The above result shows that fluorene derivative of the invention is applied in organic electroluminescence device, especially as luminous Layer and/or hole blocking layer, organic electroluminescence device is with driving voltage is low, luminous efficiency is high, with long service life excellent Point, fluorene derivative of the invention are luminous organic materials of good performance.
It should be pointed out that the present invention is particularly described with individual embodiments, but before not departing from the principle of the invention It puts, ordinary skill people can carry out the improvement on various forms or details to the present invention, these improvement also fall into this hair In bright protection scope.

Claims (10)

1. a kind of fluorene derivative, which is characterized in that its general formula of molecular structure is as shown in chemical formula I:
Wherein, any one of A in following group:
R1、R2Independently selected from cyano, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryl In any one, any one or a few in halogen atom, cyano, trifluoromethyl of the substituent group；L is selected from single Key, substituted or unsubstituted C6~C30 aryl, any one in substituted or unsubstituted C3~C30 heteroaryl；R3Selected from H, Halogen, cyano, trifluoromethyl, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl, replace or Any one in unsubstituted C3~C60 heteroaryl；R4、R5Independently selected from H, halogen, cyano, trifluoromethyl, substitution or not Substituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, appointing in substituted or unsubstituted C3~C30 heteroaryl It anticipates one kind；R6It is substituted or unsubstituted selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl C3~C30 heteroaryl in any one.
2. a kind of fluorene derivative according to claim 1, which is characterized in that L is in singly-bound or group as follows Any one:
Wherein, X is selected from CR7R8、O、S、NR9In any one；R7、R8Independently selected from H, substituted or unsubstituted C1~C10 Alkyl, substituted or unsubstituted C6~C18 aryl, any one in substituted or unsubstituted C3~C18 heteroaryl, R7、R8No It is simultaneously H, R7、R8Cyclization can be connected；R9Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C18 Any one in aryl, substituted or unsubstituted C3~C18 heteroaryl.
3. a kind of fluorene derivative according to claim 1, which is characterized in that R3、R4、R5Independently selected from H, halogen, cyanogen Base, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, sec-butyl, substituted or unsubstituted following group: phenyl, naphthalene, Anthryl, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofurans Base, dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, Quinazolyl, indyl, any one in azepine carbazyl；R6Selected from methyl, ethyl, isopropyl, tert-butyl, sec-butyl, Substituted or unsubstituted following group: phenyl, naphthalene, anthryl, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, thienyl, Benzofuranyl, benzothienyl, dibenzofuran group, dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, quinolyl, Isoquinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, quinazolyl, indyl, any one in azepine carbazyl.
4. a kind of fluorene derivative according to claim 1, which is characterized in that R1、R2Appointing in cyano or following group It anticipates one kind:
Wherein X1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11、X12、X13Independently selected from halogen, cyano, trifluoromethyl Any one.
5. a kind of fluorene derivative according to claim 1, which is characterized in that R1、R2Independently selected from cyano or following group In any one:
6. a kind of fluorene derivative according to claim 1, which is characterized in that R1、R2At least one is selected from cyano.
7. a kind of fluorene derivative according to claim 1, which is characterized in that the fluorene derivative is selected from chemistry as follows Any one in structure:
8. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes cathode, anode and is placed in One or more organic matter layers between two electrode, it is described in any item that the organic matter layer contains claim 1~7 Fluorene derivative.
9. a kind of organic electroluminescence device according to claim 8, which is characterized in that the organic matter layer includes hair Photosphere, luminescent layer include main body and doping object, are derived in the layer main body that shines containing the described in any item fluorenes of claim 1~7 Object.
10. a kind of organic electroluminescence device according to claim 8, which is characterized in that the organic matter layer includes Hole blocking layer contains the described in any item fluorene derivatives of claim 1~7 in hole blocking layer.
CN201811118218.1A 2018-09-26 2018-09-26 A kind of fluorene derivative and its organic electroluminescence device Withdrawn CN109232376A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111969120A (en) * 2020-08-28 2020-11-20 长春海谱润斯科技有限公司 Organic electroluminescent device containing fluorene derivative
CN112047872A (en) * 2020-09-18 2020-12-08 吉林奥来德光电材料股份有限公司 Organic electroluminescent fluorene compound and preparation method and application thereof
CN113801154A (en) * 2021-10-20 2021-12-17 中钢集团南京新材料研究院有限公司 Synthesis method of 9H-carbazole-2-boronic acid pinacol ester with C2-position of carbazole directly boronated by C-H
WO2022145365A1 (en) * 2020-12-28 2022-07-07 Jsr株式会社 Semiconductor substrate production method and composition
CN114957226A (en) * 2022-06-10 2022-08-30 北京八亿时空液晶科技股份有限公司 Phenanthridine derivative and application thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111969120A (en) * 2020-08-28 2020-11-20 长春海谱润斯科技有限公司 Organic electroluminescent device containing fluorene derivative
CN111969120B (en) * 2020-08-28 2021-06-22 长春海谱润斯科技股份有限公司 Organic electroluminescent device containing fluorene derivative
CN112047872A (en) * 2020-09-18 2020-12-08 吉林奥来德光电材料股份有限公司 Organic electroluminescent fluorene compound and preparation method and application thereof
CN112047872B (en) * 2020-09-18 2022-03-08 吉林奥来德光电材料股份有限公司 Organic electroluminescent fluorene compound and preparation method and application thereof
WO2022145365A1 (en) * 2020-12-28 2022-07-07 Jsr株式会社 Semiconductor substrate production method and composition
CN113801154A (en) * 2021-10-20 2021-12-17 中钢集团南京新材料研究院有限公司 Synthesis method of 9H-carbazole-2-boronic acid pinacol ester with C2-position of carbazole directly boronated by C-H
CN113801154B (en) * 2021-10-20 2024-01-26 中钢集团南京新材料研究院有限公司 Synthesis method of carbazole C2-site direct C-H boronated 9H-carbazole-2-boronic acid pinacol ester
CN114957226A (en) * 2022-06-10 2022-08-30 北京八亿时空液晶科技股份有限公司 Phenanthridine derivative and application thereof
CN114957226B (en) * 2022-06-10 2024-02-13 北京八亿时空液晶科技股份有限公司 Phenanthridine derivative and application thereof

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Application publication date: 20190118