CN108409668A - One kind containing fluorene compound and its organic electroluminescence device - Google Patents

One kind containing fluorene compound and its organic electroluminescence device Download PDF

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CN108409668A
CN108409668A CN201810533397.9A CN201810533397A CN108409668A CN 108409668 A CN108409668 A CN 108409668A CN 201810533397 A CN201810533397 A CN 201810533397A CN 108409668 A CN108409668 A CN 108409668A
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unsubstituted
substituted
base
substitution
fluorene compound
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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 one kind and containing fluorene compound and its organic electroluminescence device, is related to organic optoelectronic materials technology.The present invention connects arylamine by fluorenes human subject, substituted or unsubstituted aromatic rings condensed imidazole derivatives obtain one kind and containing fluorene compound, it is a kind of bipolar transmission material, conducive to hole and electronics in the compound of luminescent layer, with good stability and luminous efficiency, it synthesizes simple to operation, it can be applied to be used as luminescent layer dopant material in organic electroluminescence device, it can effectively solve the problems, such as in organic luminescent device that blue emitting material luminous efficiency is low, short life, its organic electroluminescence device has the advantages of luminous efficiency is high, long lifespan.

Description

One kind containing fluorene compound and its organic electroluminescence device
Technical field
The present invention relates to organic photoelectrical material technical fields, more particularly to one kind containing fluorene compound and its organic electroluminescent Device.
Background technology
Organic electroluminescent LED (OLED:Organic Light Emitting Diode) be it is a kind of utilize self-luminous The display device of phenomenon, it compared with traditional display technology, voltage characteristic, light emission luminance, luminous efficiency, device weight, Response speed and appreciative perspective etc. have significant advantage, and because of its low cost potential, become face most potential at present Plate display technology possesses broad mass market foreground.
In general, it is to generally comprise the moon that OLED, which uses stratiform or laminar structure, its structure of typical organic electroluminescence device, Pole, anode and the organic matter layer between electrode.Organic matter layer therein is primarily to improve organic electroluminescence device Efficiency and stability, include under normal circumstances：Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electronics note Enter layer etc., luminescence mechanism：Electrons and holes are injected separately into from yin, yang two-stage, organic matter is passed through by injected electrons and hole Layer transmission, exciton is compounded to form in luminescent layer, and exciton radiation transistion returns to ground state, to shine.
The luminescent layer of organic electroluminescence device generally uses the form of subject and object doping, can be shone by adjusting The type and object doping of layer material obtains the light of different demands.In order to which the color for improving display to the greatest extent is true to nature Degree, that is, it is so-called full-color, there are mainly three types of modes：First, adding colour filter using white light-emitting layer, this is to obtain panchromatic show Show simplest method.Second is that using three kinds of luminous organic materials of red, green, blue, therefore luminescent layer is three layers.Third, using blue Luminous organic material, then it is full-color with color-converting material acquisition.The second way due to independently luminous using three color of red, green, blue, It is easy to accurately control the chromatic characteristic of display device, color is also more bright-coloured true to nature.
Currently, the research of electroluminescent organic material is carried out in academia and industrial quarters extensively, a large amount of function admirables Electroluminescent organic material be developed successively, all in all, the direction of the following OLED be development high efficiency, high brightness, Long-life, inexpensive white light parts and full color display device, but the technological industrialization process still faces many keys and asks Topic, such as compared with feux rouges, green light material, for blue light material there are problems, wherein blue light material or stability is too poor；Or Luminous efficiency is too low, without practical value；Or it is difficult to the method making devices using vacuum evaporation, it can not come into operation；Or Person's luminous efficiency is roll-offed seriously, and device performance is caused integrally to deteriorate, and can not be used steadily in the long term；Therefore it develops a kind of efficient, steady Fixed blue emitting material becomes industry urgent problem to be solved.
Invention content
The object of the present invention is to provide one kind containing fluorene compound and its organic electroluminescence device, provided by the invention to contain fluorenes Compound has higher luminous efficiency, and thermal stability is good, and good film-forming property, synthetic method is simple to operation, contains fluorenes using this Closing organic electroluminescence device prepared by object, there is good luminous efficiency and service life to show.
The present invention provides one kind containing fluorene compound, and general formula of molecular structure is as shown in chemical formula I：
Wherein, R1、R2Independently selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 One kind in aryl, substituted or unsubstituted C3~C60 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~ One kind in C30 alkyl, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted C3~C60 heteroaryls；A is selected from and takes Generation or unsubstituted C6~C60 aryl；L is selected from singly-bound, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3 One kind in~C30 heteroaryls.
Preferably, R1、R2Independently selected from H, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~ One kind in C30 aryl, substituted or unsubstituted C3~C30 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1 One kind in~C10 alkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls；A is selected from Substituted or unsubstituted C6~C30 aryl；L is selected from singly-bound, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted One kind in C3~C24 heteroaryls.
Further preferably, A be selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenanthryl, Any one in substituted or unsubstituted pyrenyl.
Further preferably, R1、R2Independently selected from the alkyl of C1~C10, substituted or unsubstituted phenyl, substituted or unsubstituted Naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substitution do not take The acridinyl in generation, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine thiophene It is base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted Ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridyl group, substitution or not Substituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, Substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substitution do not take The thienyl in generation, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzo furan Any one muttered in base, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group.
Further preferably, Ar1、Ar2Independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or not Substituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted acridinyl, takes substituted or unsubstituted phenanthryl Generation or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine thiophene base, replace or do not take substituted or unsubstituted phenothiazinyl The fluorenyl in generation, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted ferrosin base, substitution Or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, It is substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted Pyrrole radicals, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, takes substituted or unsubstituted benzopyrrole base Generation or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substitution or not Any one in substituted dibenzothiophene, substituted or unsubstituted dibenzofuran group.
Further preferably, L is selected from singly-bound, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted Anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substitution do not take The pyrazinyl in generation, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole radicals, takes substituted or unsubstituted pyridazinyl Generation or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, substitution or unsubstituted Furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted hexichol Any one in bithiophene base, substituted or unsubstituted dibenzofuran group.
Most preferably, any one containing fluorene compound in chemical constitution as follows of the present invention：
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device successively include cathode, Organic matter layer, anode；The organic matter layer is between the cathode and anode, and at least one layer contains in the organic matter layer It is of the present invention any containing fluorene compound.
Preferably, the organic matter layer includes luminescent layer, is contained in luminescent layer of the present invention any containing fluorenes Close object.
Beneficial effects of the present invention：
The present invention provides a kind of containing fluorene compound and its organic electroluminescence device.The present invention passes through on 2,7 of fluorenes Connection arylamine and substituted or unsubstituted aromatic rings condensed imidazole class ligand obtain it is described contain fluorene compound, wherein aromatic rings is thick Closing imidazole group, there is certain electrophilic characteristic, arylamine to have certain cavity transmission ability, finally obtained chemical combination containing fluorenes Object is a kind of bipolar materials, has good electronics and cavity transmission ability, can effectively improve the electron transport ability of material, Improve hole and electronics luminescent layer recombination rate, to improve the luminous efficiency of its organic luminescent device.
The conjugation of aromatic rings condensed imidazole base is big, and rigidity is strong, is connect with fluorenes as ligand, can improve the steady of material itself It is qualitative.
The present invention adjusts molecular weight, to carry by connecting arylamine, aromatic rings condensed imidazole ligand in 2,7 sites of fluorenes The glass transition temperature of high material and be not easy to crystallize, be easy to form a film.
In addition arylamine, aromatic rings condensed imidazole connect with fluorenes can be improved molecule HOMO and LUMO energy gaps it is poor, make material Luminescent spectrum blue shift obtains more saturated blue colors.
The organic electroluminescence device using the present invention prepared containing fluorene compound, has good luminous efficiency and use Service life shows.
Preparation method containing fluorene compound of the present invention is simple, and raw material is easy to get, and disclosure satisfy that industrialization demand.
Specific implementation mode：
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 The every other embodiment that personnel are obtained without making creative work, belongs to protection scope of the present invention.
Aryl of the present invention refer to aromatic hydrocarbon molecule aromatic core carbon on remove a hydrogen atom after, be left univalent perssad it is total 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 not limited to oxygen, sulphur, nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl Or fused ring heteroaryl, example may include pyridyl group, pyrimidine radicals, triazine radical, indyl, quinolyl, isoquinolyl, benzothiophene Base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
The present invention provides one kind containing fluorene compound, and general formula of molecular structure is as shown in chemical formula I：
Wherein, R1、R2Independently selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 One kind in aryl, substituted or unsubstituted C3~C60 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~ One kind in C30 alkyl, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted C3~C60 heteroaryls；A is selected from and takes Generation or unsubstituted C6~C60 aryl；L is selected from singly-bound, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3 One kind in~C30 heteroaryls.
According to the present invention, in the substituted alkyl, substituted aryl, substituted heteroaryl, the substituent group is independently Selected from deuterium, CN, halogen atom, CF3, C1~C10 alkyl, C6~C24 aryl or C3~C20 heteroaryls.
Preferably, R1、R2Independently selected from H, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~ One kind in C30 aryl, substituted or unsubstituted C3~C30 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1 One kind in~C10 alkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls；A is selected from Substituted or unsubstituted C6~C30 aryl；L is selected from singly-bound, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted One kind in C3~C24 heteroaryls.
Further preferably, A be selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenanthryl, Any one in substituted or unsubstituted pyrenyl.
Further preferably, R1、R2Independently selected from the alkyl of C1~C10, substituted or unsubstituted phenyl, substituted or unsubstituted Naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substitution do not take The acridinyl in generation, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine thiophene It is base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted Ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridyl group, substitution or not Substituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, Substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substitution do not take The thienyl in generation, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzo furan Any one muttered in base, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group.
Further preferably, Ar1、Ar2Independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or not Substituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted acridinyl, takes substituted or unsubstituted phenanthryl Generation or unsubstituted phenoxazine base, substituted or unsubstituted phenoxazine thiophene base, replace or do not take substituted or unsubstituted phenothiazinyl The fluorenyl in generation, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted ferrosin base, substitution Or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, It is substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted Pyrrole radicals, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, takes substituted or unsubstituted benzopyrrole base Generation or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substitution or not Any one in substituted dibenzothiophene, substituted or unsubstituted dibenzofuran group.
Further preferably, L is selected from singly-bound, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted Anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substitution do not take The pyrazinyl in generation, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole radicals, takes substituted or unsubstituted pyridazinyl Generation or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, substitution or unsubstituted Furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted hexichol Any one in bithiophene base, substituted or unsubstituted dibenzofuran group.
Most preferably, as an example, it is not particularly limited, it is of the present invention to be selected from chemistry knot as follows containing fluorene compound Any one in structure：
The present invention's is obtained containing fluorene compound by following synthetic route：
When A is substituted or unsubstituted benzene
When A be it is substituted or unsubstituted how, luxuriant and rich with fragrance, pyrene
Wherein, R1、R2、R3Independently selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~ One kind in C60 aryl, substituted or unsubstituted C3~C60 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1 One kind in~C30 alkyl, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted C3~C60 heteroaryls；A is selected from Substituted or unsubstituted C6~C60 aryl；L is selected from singly-bound, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted One kind in C3~C30 heteroaryls.
Specific synthesis step is as follows：
1, raw material a-1, a-2, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, anti-by Buchwald It should obtain intermediate b-1；
2, raw material a-3, a-4 is alkali by catalyst, NaOH of tetra-n-butyl ammonium bromide, and intermediate b-2 is obtained by the reaction；
3, intermediate b-2, b-1, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, passes through Buchwald Intermediate b-4-1 is obtained by the reaction (L is singly-bound)；
4, intermediate b-2, connection boric acid pinacol fat, with Pd (PPh3)4For catalyst, K2CO3For alkali, centre is obtained by the reaction Body b-3；Intermediate b-3, raw material a-5, with Pd (PPh3)4For catalyst, K2CO3For alkali.Intermediate is obtained by the reaction by Suzuki B-4-2 (L is not singly-bound)；
5, combining step 3,4, its general formula of intermediate b-4-1, b-4-2 are unified for b-4；
6, when A is substituted or unsubstituted benzene：Raw material a-6, a-7 are with Pd (PPh3)4For catalyst, K2CO3For alkali.Pass through Intermediate b-5 is obtained by the reaction in Suzuki；Intermediate b-5, b-4, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is Chemical compounds I -1 is obtained by the reaction by Buchwald in alkali；
7, when A is substituted or unsubstituted naphthalene, phenanthrene, pyrene：Intermediate b-3, HAS (hydroxylamine-o-sulfonic acid), using MeCN as molten Agent, NaOH are alkali, obtain intermediate b-6-1；Intermediate b-4-1, raw material a-8, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, and intermediate b-6-2 is obtained by the reaction by Buchwald；Its general formula of intermediate b-6-1, b-6-2 is unified for b-6； Intermediate b-6, raw material a-9, a-10, CH3COONH2, in CH3Under COOH reaction environments, product I -2 is obtained by the reaction.
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 successively include cathode, Organic matter layer, anode；The organic matter layer is between the cathode and anode, and at least one layer contains in the organic matter layer It is of the present invention any containing fluorene compound.
Preferably, the organic matter layer includes luminescent layer, contains fluorene compound containing of the present invention in the luminescent layer.
Most preferably, luminescent layer contains subject and object, at least contains in object a kind of of the present invention containing fluorene compound.
Organic electroluminescence device structure of the present invention is followed successively by：ITO is as transparent anode；2-TNATA is as empty Cave implanted layer；NPB is as hole transmission layer；The ADN/ present invention's is used as luminescent layer substance containing fluorene compound；Alq3As electronics Transport layer；LiF is used as electron injecting layer；Al is used as cathode, of the present invention to be adulterated as luminescent layer object containing fluorene compound Substance.
It is of the present invention to be located at luminescent layer containing fluorene compound, it is same as below to have manufactured as object dopant material The organic electroluminescence device of construction：
ITO/2-TNATA(60nm)/NPB(30nm)/ADN：It is of the present invention to contain fluorene compound (30nm)/Alq3 (20nm)/LiF(1nm)/Al(200nm)。
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 1
Step1：Aniline (0.75g, 8mmol), bromobenzene (1.05,6.67mmol), 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, It is reacted under the conditions of 100 DEG C for 24 hours, ether and water is used to extract organic phase after reaction, organic layer is dried with MgSO4, and concentration is organic Object crosses column chromatography, is recrystallized to give intermediate 1-1 (0.88g, 78%).
Step2：Under room temperature, 2,7- dibromos fluorenes (9.72g, 30mmol), tetra-n-butyl ammonium bromide are added in reactor (0.08g, 0.25mmol), iodomethane (12.77g, 90mmol), 50% NaOH solution 10mL, DMSO 120mL, ultrasonic reaction 5h, the rear 500mL water that is added stop reaction, stir, filter, washing, being dried to obtain intermediate 1-2 (10.46g, 99%).
Step3：In reactor be added intermediate 1-1 (1.35g, 8mmol), intermediate 1-2 (2.35g, 6.67mmol), 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, ether and water is used to extract organic phase after reaction, and organic layer is dried with MgSO4, Condensed organic crosses column chromatography, is recrystallized to give intermediate 1-3 (2.2g, 75%).
Step4：Intermediate 1-3 (4.4g, 10mmol), connection boric acid pinacol fat are added under nitrogen protection, in reactor (3.81g, 15mmol), K2CO3Solution (16mL, 2mol/L), Pd (PPh3)4(0.21g, 0.18mmol), 48h is reacted at 90 DEG C, Separating-purifying obtains intermediate 1-4 (3.9g, 80%).
Step5：In reactor be added intermediate 1-4 (4.87g, 10mmol), hydroxylamine-o-sulfonic acid (HAS) (1.7g, 15mmol), acetonitrile 60mL, NaOH (1.09g, 27.5mmol), after be stirred to react 18h, it is heavy to be centrifugally separating to obtain after reaction It forms sediment, deionized water washing is placed in acetonitrile and hexane solution, ultrasonic 15min, separating-purifying obtains intermediate 1-5 (3.05g, 81%).
Step6：Under nitrogen protection, be added in reactor 1,2- naphthoquinones (1.58g, 10mmol), benzaldehyde (1.06g, 10mmol), intermediate 1-5 (3.77g, 10mmol), ammonium acetate (3.75g, 50mmol), acetic acid 100mL, 120 DEG C of heating of oil bath Flow back 12h, and distilled water is added after reaction and stops reaction, filtering is washed with water, glacial acetic acid, ethyl alcohol successively, is dried, rear pillar Chromatography obtains compound 1 (4.59g, 76%).
The synthesis of [embodiment 2] compound 73
Step1：73-1 is obtained with reference to 1 compound of embodiment, 1 synthetic method Step1；
Step2：73-2 is obtained with reference to 1 compound of embodiment, 1 synthetic method Step3；
Step3：2- chlorobenzenes are added under nitrogen protection, in reaction vessel and dislike imidazoles (1.41g, 9.2mmol), phenyl boric acid (1.02g, 8.4mmol), tetra-triphenylphosphine palladium (0.09g, 0.08mmol), potassium carbonate (3.48g, 25.2mmol), toluene 60mL, Ethyl alcohol 20mL and distilled water 20mL stirs 3h under the conditions of 120 DEG C.Distilled water stops reaction, ethyl acetate after reaction terminates Extraction, organic layer MgSO4Dry, solvent is removed in vacuum distillation, is purified to obtain intermediate 73-3 later with silica gel column chromatography (1.22g, 75%).
Step4：In reactor be added intermediate 73-3 (1.55g, 8mmol), intermediate 73-2 (2.94,6.67mmol), 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, ether and water is used to extract organic phase after reaction, and organic layer is dried with MgSO4, Condensed organic crosses column chromatography, is recrystallized to give compound 73 (2.74g, 74%).
The synthesis of [embodiment 3] compound 119
Step1：119-1 is obtained with reference to 1 compound of embodiment, 1 synthetic method Step2；
Step2：119-2 is obtained with reference to 1 compound of embodiment, 1 synthetic method Step3；
Step3：119-3 is obtained with reference to 2 compound of embodiment, 73 synthetic method Step3；
Step4：119-4 is obtained with reference to 2 compound of embodiment, 73 synthetic method Step3；
Step5：119 (3.36g, 70%) are obtained with reference to 2 compound of embodiment, 73 synthetic method Step4.
The synthesis of [embodiment 4] compound 133
Compound 133 (5.21g, 74%) is obtained according to the synthetic method of compound 1.
The synthesis of [embodiment 5] compound 139
Compound 139 (5.21g, 70%) is obtained according to the synthetic method of compound 1.
The synthesis of [embodiment 6] compound 181
Compound 181 (4.88g, 72%) is obtained according to the synthetic method of compound 1.
The synthesis of [embodiment 7] compound 234
Step1：P-phenylenediamine (0.87g, 8mmol), intermediate 1-3 (2.94g, 6.67mmol), 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, uses ether and water to extract organic phase after reaction, organic layer is dried with MgSO4, dense Contracting organic matter crosses column chromatography, is recrystallized to give compound 234-1 (2.23g, 74%).
Step2：Under nitrogen protection, be added in reactor 1,2- naphthoquinones (1.58g, 10mmol), benzaldehyde (1.06g, 10mmol), intermediate 234-1 (4.53g, 10mmol), ammonium acetate (3.75g, 50mmol), acetic acid 100mL, 120 DEG C of oil bath add Heat reflux 12h is added distilled water and stops reaction after reaction, and filtering is washed with water, glacial acetic acid, ethyl alcohol successively, is dried, after Column chromatography obtains compound 234 (4.76g, 70%).
The synthesis of [embodiment 8] compound 237
Step1：Under nitrogen protection, intermediate 1-4 (4.09g, 8.4mmol) ,-two bromo chlorine of Isosorbide-5-Nitrae are added in reaction vessel (2.63g, 9.2mmol), tetra-triphenylphosphine palladium (0.09g, 0.08mmol), potassium carbonate (3.48g, 25.2mmol), toluene 60mL, Ethyl alcohol 20mL and distilled water 20mL stirs 3h under the conditions of 120 DEG C.Distilled water stops reaction, ethyl acetate after reaction terminates Extraction, organic layer MgSO4Dry, solvent is removed in vacuum distillation, is purified to obtain intermediate 237-1 later with silica gel column chromatography (3.47g, 73%).
Step2：Under nitrogen protection, 2-Chlorobenzimidazole (1.28g, 8.4mmol), phenyl boric acid are added in reaction vessel (1.12g, 9.2mmol), tetra-triphenylphosphine palladium (0.09g, 0.08mmol), potassium carbonate (3.48g, 25.2mmol), toluene 60mL, Ethyl alcohol 20mL and distilled water 20mL stirs 3h under the conditions of 120 DEG C.Distilled water stops reaction, ethyl acetate after reaction terminates Extraction, organic layer MgSO4Dry, solvent is removed in vacuum distillation, is purified to obtain intermediate 237-2 later with silica gel column chromatography (1.21g, 74%).
Step3：In reactor be added intermediate 237-2 (1.55g, 8mmol), intermediate 237-1 (3.78g, 6.67mmol)、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, and ether and water is used to extract organic phase after reaction, organic Layer is dried with MgSO4, condensed organic, is crossed column chromatography, is recrystallized to give compound 237 (3.13g, 69%).
The values of FD-MS containing fluorene compound of synthesis of the embodiment of the present invention are as shown in table 1：
【Table 1】
Embodiment FD-MS
Embodiment 1 M/z=603.31 (C44H33N3=603.27)
Embodiment 2 M/z=554.21 (C39H30N4=554.25)
Embodiment 3 M/z=719.36 (C53H41N3=719.33)
Embodiment 4 M/z=703.27 (C52H37N3=703.30)
Embodiment 5 M/z=743.34 (C54H37N3O=743.29)
Embodiment 6 M/z=677.31 (C50H35N3=677.28)
Embodiment 7 M/z=679.28 (C50H37N3=679.30)
Embodiment 8 M/z=679.33 (C50H37N3=679.30)
[comparative example 1] device prepares embodiment：
Ito glass substrate is placed in distilled water and is cleaned 2 times, ultrasonic washing 30 minutes is 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 is successively deposited on the ito transparent electrode being already prepared to, vapor deposition hole passes Defeated layer NPB/30nm, vapor deposition main body A DN：Adulterate 3% mixing of DPAVBi/30nm and then vapor deposition electron transfer layer Alq3/20nm、 Electron injecting layer LiF/1nm, cathode Al/200nm.
[embodiment 9] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 1 of embodiment 1.
[embodiment 10] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 73 of embodiment 2.
[embodiment 11] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 119 of embodiment 3.
[embodiment 12] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 133 of embodiment 4.
[embodiment 13] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 139 of embodiment 5.
[embodiment 14] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 181 of embodiment 6.
[embodiment 15] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 234 of embodiment 7.
[embodiment 16] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 237 of embodiment 8.
The characteristics of luminescence test result such as table 2 of luminescent device prepared by 9-16 of the embodiment of the present invention and comparative example 1 It is shown.
[table 2]
The above result shows that of the invention is applied to containing fluorene compound in organic luminescent device, especially as blue light visitor The cut-in voltage of body dopant, organic electroluminescence electro-optical device is substantially reduced, and luminous efficiency and service life are also significantly increased, this Invention is luminous organic material of good performance containing fluorene compound.
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 present invention improvement on various forms or details, these improvement also fall into this hair In bright protection domain.

Claims (9)

1. one kind containing fluorene compound, which is characterized in that its general formula of molecular structure is as shown in chemical formula I：
Wherein, R1、R2Independently selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl, One kind in substituted or unsubstituted C3~C60 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C30 alkane One kind in base, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted C3~C60 heteroaryls；A be selected from substitution or Unsubstituted C6~C60 aryl；L is selected from singly-bound, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 One kind in heteroaryl.
2. according to claim 1 a kind of containing fluorene compound, which is characterized in that R1、R2It does not take independently selected from H, substitution or One in C1~C10 alkyl in generation, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls Kind；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, substitution or One kind in unsubstituted C3~C30 heteroaryls；A is selected from substituted or unsubstituted C6~C30 aryl；L be selected from singly-bound, substitution or One kind in unsubstituted C6~C24 aryl, substituted or unsubstituted C3~C24 heteroaryls.
3. according to claim 1 a kind of containing fluorene compound, which is characterized in that A is selected from substituted or unsubstituted phenyl, takes Generation or unsubstituted naphthalene, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl in any one.
4. according to claim 1 a kind of containing fluorene compound, which is characterized in that R1、R2Independently selected from the alkane of C1~C10 Base, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthrene Base, substituted or unsubstituted triphenylene, substituted or unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, substitution or Unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazole Base, substituted or unsubstituted pyrenyl, substituted or unsubstituted ferrosin base, substituted or unsubstituted base, substitution or unsubstituted Acenaphthenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substitution or Unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzo pyrrole Cough up base, substituted or unsubstituted triazolyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substitution or not Substituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzothiophene, substitution or not Any one in substituted dibenzofuran group.
5. according to claim 1 a kind of containing fluorene compound, which is characterized in that Ar1、Ar2It does not take independently selected from substitution or The phenyl in generation, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substitution do not take The triphenylene in generation, substituted or unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenthazine Base, substituted or unsubstituted phenoxazine thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substitution do not take The pyrenyl in generation, substituted or unsubstituted ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substitution or Unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazine Base, substituted or unsubstituted triazine radical, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substitution or Unsubstituted triazolyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzo thiophene Pheno base, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzo Any one in furyl.
6. according to claim 1 a kind of containing fluorene compound, which is characterized in that L is selected from singly-bound, substituted or unsubstituted benzene Base, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrrole Piperidinyl, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substitution or not Substituted triazine radical, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazole Base, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substitution or In unsubstituted benzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group Any one.
7. according to claim 1 a kind of containing fluorene compound, which is characterized in that described to be selected from as follows containing fluorene compound Any one in chemical constitution：
8. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes cathode, organic matter successively Layer, anode；The organic matter layer is between the cathode and anode, and at least one layer contains and has the right to want in the organic matter layer 1~7 any one of them is asked to contain fluorene compound.
9. according to a kind of organic electroluminescence device described in claim 8, which is characterized in that the organic matter layer includes hair Photosphere contains fluorene compound in luminescent layer containing claim 1~7 any one of them.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073307A (en) * 2022-07-27 2022-09-20 上海钥熠电子科技有限公司 Fluorene compound and application thereof in organic electroluminescent device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115073307A (en) * 2022-07-27 2022-09-20 上海钥熠电子科技有限公司 Fluorene compound and application thereof in organic electroluminescent device
CN115073307B (en) * 2022-07-27 2024-04-19 上海钥熠电子科技有限公司 Fluorene compound and application thereof in organic electroluminescent device

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Application publication date: 20180817