CN108774177A - One kind containing Benzofluorene compound and its organic luminescent device - Google Patents

One kind containing Benzofluorene compound and its organic luminescent device Download PDF

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CN108774177A
CN108774177A CN201810533361.0A CN201810533361A CN108774177A CN 108774177 A CN108774177 A CN 108774177A CN 201810533361 A CN201810533361 A CN 201810533361A CN 108774177 A CN108774177 A CN 108774177A
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unsubstituted
substituted
base
substitution
aryl
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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 Benzofluorene compound and its organic luminescent device, is related to organic optoelectronic materials technology.The present invention connects arylamine, substituted or unsubstituted aromatic rings condensed imidazole, oxazole derivatives by benzfluorene human subject and obtains one kind containing Benzofluorene 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 luminescent 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 luminescent device has the advantages of luminous efficiency is high, long lifespan.

Description

One kind containing Benzofluorene compound and its organic luminescent device
Technical field
The present invention relates to organic photoelectrical material technical fields, more particularly to one kind containing Benzofluorene compound and its organic light emission Device.
Background technology
Organic Light Emitting Diode (OLED:Organic Light Emitting Diode) it is a kind of spontaneous optical phenomenon of utilization Display device, it is compared with traditional display technology, in 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, and the panel for becoming most potential at present is aobvious Show technology, possesses broad mass market foreground.
In general, it is to generally comprise cathode, sun that OLED, which uses stratiform or laminar structure, its structure of typical organic luminescent device, Pole and the organic matter layer between electrode.Organic matter layer therein is primarily to improve the efficiency of organic luminescent device and steady It is qualitative, include under normal circumstances：Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer etc., hair Ray machine is managed：Electrons and holes are injected separately into from yin, yang two-stage, are transmitted by organic matter layer by injected electrons and hole, are being sent out Photosphere is compounded to form exciton, and exciton radiation transistion returns to ground state, to shine.
The luminescent layer of organic luminescent device generally uses the form of subject and object doping, can be by adjusting luminescent layer material The type and object doping of material obtains the light of different demands.In order to improve the color fidelity of display to the greatest extent, It is exactly so-called full-color, there are mainly three types of modes：First, adding colour filter using white light-emitting layer, this is that acquisition total colouring is most simple Single method.Second is that using three kinds of luminous organic materials of red, green, blue, therefore luminescent layer is three layers.Third, using the organic hair of blue Luminescent material, then it is full-color with color-converting material acquisition.The second way using three color of red, green, blue due to independently being shone, it is easy to The chromatic characteristic of display device is accurately controlled, color is also more bright-coloured true to nature.
Currently, the research of luminous organic material is carried out in academia and industrial quarters extensively, a large amount of function admirables have Electroluminescent material is developed successively, and all in all, the direction of the following OLED is development high efficiency, high brightness, longevity The white light parts and full color display device of life, low cost, but the technological industrialization process still faces many critical issues, 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 it shines 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 hair Light 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, stabilization Blue emitting material becomes industry urgent problem to be solved.
Invention content
The object of the present invention is to provide one kind containing Benzofluorene compound and its organic luminescent device, provided by the invention to contain benzene And fluorene compound has higher luminous efficiency, thermal stability is good, and good film-forming property, synthetic method is simple to operation, is contained using this There is organic luminescent device prepared by Benzofluorene compound good luminous efficiency and service life to show.
The present invention provides one kind containing Benzofluorene compound, and general formula of molecular structure is as shown in chemical formula I：
Wherein, A is selected from substituted or unsubstituted C6~C60 aryl；X is selected from NR2, any one in O；R1、R2Independently Selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted C3~ One kind in C60 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6 One kind in~C60 aryl, substituted or unsubstituted C3~C60 heteroaryls；L is selected from singly-bound, substituted or unsubstituted C6~C30 One kind in aryl, substituted or unsubstituted C3~C30 heteroaryls.
Preferably, A is selected from substituted or unsubstituted C6~C30 aryl；X is selected from NR2, any one in O；R1、R2It is independent Ground is selected from H, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3 One kind in~C30 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted One kind in C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls；L be selected from singly-bound, substituted or unsubstituted C6~ One kind in C24 aryl, substituted or unsubstituted 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 Benzofluorene compound in chemical constitution as follows of the present invention：
The present invention also provides a kind of organic luminescent device, the organic luminescent device successively include cathode, organic matter layer, Anode；The organic matter layer is at least one layer of in the organic matter layer to contain institute of the present invention between the cathode and anode That states is any containing Benzofluorene compound.
Preferably, the organic matter layer includes luminescent layer, is contained in luminescent layer of the present invention any containing benzo Fluorene compound.
Beneficial effects of the present invention：
The present invention provides a kind of containing Benzofluorene compound and its organic luminescent device.The present invention passes through in 7H- benzfluorenes 5,9 upper connection arylamine and substituted or unsubstituted aromatic rings is thick and imidazoles, oxazole class ligand obtain described containing benzfluorene Object is closed, wherein aromatic rings is thick and there is certain electrophilic characteristic, arylamine to have certain hole transport energy for imidazoles, oxazole group Power, the finally obtained Benzofluorene compound that contains is a kind of bipolar materials, has good electronics and cavity transmission ability, can have Effect improves the electron transport ability of material, improve hole and electronics luminescent layer recombination rate, to improve its organic illuminator The luminous efficiency of part.
Aromatic rings is thick and imidazoles, the conjugation of oxazolyl are big, and rigidity is strong, connect, can be improved with 7H- benzfluorenes as ligand The stability of material itself.
Arylamine, aromatic rings are thick and imidazoles, oxazole ligand, adjusting divide by being connected in 5,9 sites of 7H- benzfluorenes by the present invention Son amount, is not easy to crystallize, is easy to form a film to improve the glass transition temperature of material.
In addition arylamine, aromatic rings be thick and imidazoles or oxazole connect HOMO the and LUMO energy that molecule can be improved with 7H- benzfluorenes Gap is poor, makes the luminescent spectrum blue shift of material, obtains more saturated blue colors.
The organic luminescent device using the present invention prepared containing Benzofluorene compound, has good luminous efficiency and use Service life shows.
Preparation method containing Benzofluorene 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 Benzofluorene compound, and general formula of molecular structure is as shown in chemical formula I：
Wherein, A is selected from substituted or unsubstituted C6~C60 aryl；X is selected from NR2, any one in O；R1、R2Independently Selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted C3~ One kind in C60 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6 One kind in~C60 aryl, substituted or unsubstituted C3~C60 heteroaryls；L is selected from singly-bound, substituted or unsubstituted C6~C30 One kind in aryl, substituted or unsubstituted C3~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, A is selected from substituted or unsubstituted C6~C30 aryl；X is selected from NR2, any one in O；R1、R2It is independent Ground is selected from H, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3 One kind in~C30 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted One kind in C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls；L be selected from singly-bound, substituted or unsubstituted C6~ One kind in C24 aryl, substituted or unsubstituted 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 as followsization containing Benzofluorene compound Learn any one in structure：
The present invention's is obtained containing Benzofluorene compound by following synthetic route：
Wherein, A is selected from substituted or unsubstituted C6~C60 aryl；X is selected from NR2, any one in O；R1、R2、R3Solely On the spot it is selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted One kind in C3~C60 heteroaryls；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C30 alkyl, substitution or unsubstituted C6~C60 aryl, one kind in substituted or unsubstituted C3~C60 heteroaryls；L is selected from singly-bound, substituted or unsubstituted C6 One kind in~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls.
Specific synthesis step is as follows：
1, raw material a-1, R1- I is alkali by catalyst, NaOH of tetra-n-butyl ammonium bromide, and intermediate b-1 is obtained by the reaction；
2, intermediate b-1, NBS brominations obtain intermediate b-2；
3, intermediate b-2, I2, acid iodide, acetic acid, sulfuric acid, iodate obtains intermediate b-3；
4, raw material a-2, a-3, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, anti-by Buchwald It should obtain intermediate b-4；
5, intermediate b-4, b-3, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, passes through Buchwald Intermediate b-5 is obtained by the reaction；
6, when L is singly-bound, intermediate b-5, join boric acid pinacol fat, with Pd (PPh3)4For catalyst, K2CO3For alkali, Intermediate b-6-1 is obtained by the reaction；When L is not singly-bound, intermediate b-5, raw material a-4, with Pd (PPh3)4For catalyst, K2CO3 For alkali, intermediate b-6-2 is obtained by the reaction by Suzuki；
7, (1) when A be substituted or unsubstituted phenyl, X=NR2：Raw material a-5 and a-6, with Pd2(dba)3、P(t-Bu)3 For catalyst, NaOBu-t is alkali, and intermediate b-7 is obtained by the reaction by Buchwald；Intermediate b-7, b-6-1, with Pd (PPh3)4 For catalyst, K2CO3For alkali, product I -1 is obtained by the reaction by Suzuki；Or intermediate b-7, b-7-2, with Pd (PPh3)4To urge Agent, K2CO3For alkali, product I -1 is obtained by the reaction by Suzuki.
(2) when A is substituted or unsubstituted phenyl, X=O：Raw material a-7, intermediate b-6-1, with Pd (PPh3)4For catalysis Agent, K2CO3For alkali, product I -1 is obtained by the reaction by Suzuki；Raw material a-7, intermediate b-6-2, with Pd (PPh3)4For catalysis Agent, K2CO3For alkali, product I -1 is obtained by the reaction by Suzuki.
8, intermediate b-6-1, raw material a-8, with Pd (PPh3)4For catalyst, K2CO3For alkali, it is obtained by the reaction by Suzuki Intermediate b-8 (L is not singly-bound)；
9, intermediate b-5 or b-8 obtains lithium reagent with n-Buli exchange reactions, after continue that intermediate b-9 (L are obtained by the reaction For singly-bound, or it is not singly-bound)；
10, (1) when A be substituted or unsubstituted naphthalene, phenanthrene, pyrene, X=NR2：Intermediate b-9, raw material a-9, a-10, acetic acid Ammonium, under the conditions of acetic acid, product I -2 is obtained by the reaction.
(2) when A is substituted or unsubstituted naphthalene, phenanthrene, pyrene, X=O：Intermediate b-9, raw material a-9, ammonium hydrogen carbonate, react To product I -3.
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 luminescent device, the organic luminescent device successively include cathode, organic matter layer, Anode；The organic matter layer is at least one layer of in the organic matter layer to contain institute of the present invention between the cathode and anode That states is any containing Benzofluorene compound.
Preferably, the organic matter layer includes luminescent layer, contains benzfluorene containing of the present invention in the luminescent layer Close object.
Most preferably, luminescent layer contains subject and object, at least contains in object a kind of of the present invention containing benzfluorene Close object.
OLED structure of the present invention is followed successively by：ITO is as transparent anode；2-TNATA is noted as hole Enter layer；NPB is as hole transmission layer；The ADN/ present invention's is used as luminescent layer substance containing Benzofluorene compound；Alq3As electronics Transport layer；LiF is used as electron injecting layer；Al is used as cathode, of the present invention to be used as luminescent layer object containing Benzofluorene compound Dopant.
It is of the present invention to be located at luminescent layer containing Benzofluorene compound, it is following to have manufactured as object dopant material The organic luminescent device of same structure：
ITO/2-TNATA(60nm)/NPB(30nm)/ADN：It is of the present invention to contain Benzofluorene compound (30nm)/Alq3
(20nm)/LiF(1nm)/Al(200nm)。
Organic luminescent device of the present invention can be widely applied to Display panel, lighting source, flexibility OLED, Electronic Paper, The fields such as Organophotoreceptor or Organic Thin Film Transistors, direction board, signal lamp.
The synthesis of [embodiment 1] compound 2
Step1：Under room temperature, 7H- benzfluorenes (6.49g, 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 2-1 (7.26g, 99%).
Step2：Under nitrogen protection, in reactor be added intermediate 2-1 (2.44g, 10mmol), NBS (1.78g, 10mmol), acetic acid 50mL is stirred to react 1h at 70 DEG C, and postcooling to room temperature adds aqueous solution of sodium bisulfite, after use acetic acid Ethyl ester liquid separation boils off the solvent under reduced pressure of organic layer, the cleaning of obtained crude product with methanol, after recrystallized from heptane, then It is recrystallized in ethyl acetate/alcohol mixed solution, obtains intermediate 2-2 (2.68g, 83%).
Step3：Under nitrogen protection, intermediate 2-2 (3.23g, 10mmol), I are added in reactor2(1.02g, 4mmol), Acid iodide (0.88g, 5mmol), acetic acid 60mL, sulfuric acid 2mL, 120 DEG C are stirred to react 2h, it is rear it is cold go to room temperature, add bisulfite Sodium water solution stopping reaction, rear that sodium carbonate neutralisation of sulphuric acid is added, follow-up to carry out liquid separation with toluene and water, organic layer is evaporated under reduced pressure, The crude product of acquisition crosses silica gel column purification and obtains intermediate 2-3 (3.05g, 68%).
Step4：In reactor be added aniline (0.75g, 8mmol), bromo- 1, the 1'- biphenyl (1.55g, 6.67mmol) of 4-, 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 2-4 (1.24g, 76%).
Step5：In reactor be added intermediate 2-4 (1.96g, 8mmol), intermediate 2-3 (3.00g, 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 2-5 (2.72g, 72%).
Step6：Intermediate 2-5 (5.67g, 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 2-6 (4.79g, 78%).
Step7：In reactor be added bromobenzene (1.26g, 8mmol), the chloro- 1H- benzimidazoles (1.02g, 6.67mmol) of 2-, 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 2-7 (1.17g, 77%)
Step8：Under nitrogen protection, intermediate 2-7 (2.10g, 9.2mmol), intermediate 2-6 are added in reaction vessel (5.15g, 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 compound 2 later with silica gel column chromatography (4.28g, 75%).
The synthesis of [embodiment 2] compound 53
Compound 53 (3.90g, 72%) is obtained according to the synthetic method of compound 2.
The synthesis of [embodiment 3] compound 93
Step1：Intermediate 93-1 is obtained with reference to the method for 1 compound of embodiment, 2 synthesis step Step4.
Step2：Intermediate 93-2 is obtained according to the method for 1 compound of embodiment, 2 synthesis step Step5.
Step3：In reactor be added intermediate 93-2 (5.41g, 10mmol), THF 50mL, after be cooled to -78 DEG C, add Enter n-Buli (0.64g, 10mmol), stir 1h, after be to slowly warm up to room temperature, DMF (1.83g, 25mmol) is added, is stirred at room temperature 3h is reacted, extracts organic phase afterwards, silicagel column is crossed and obtains intermediate 93-3 (3.33g, 68%).
Step4：Under nitrogen protection, be added in reactor 1,2- naphthoquinones (2.37g, 15mmol), intermediate 93-3 (4.9g, 10mmol), aniline (2.24g, 12mmol), ammonium acetate (0.75g, 100mmol), glacial acetic acid 100mL, back flow reaction are for 24 hours, cooling To room temperature, reactant is poured into methanol solution, stirred, detached, filtered, cleaned, being dried to obtain compound 93 (5.42g, 77%).
The synthesis of [embodiment 4] compound 135
Compound 135 (5.80g, 73%) is obtained according to the synthetic method of compound 93.
The synthesis of [embodiment 5] compound 157
Compound 157 (5.17g, 71%) is obtained according to the synthetic method of compound 93.
The synthesis of [embodiment 6] compound 173
Compound 173 (5.03g, 69%) is obtained according to the synthetic method of compound 93.
The synthesis of [embodiment 7] compound 214
Step1：Intermediate 214-1 is obtained with reference to the method for 3 compound of embodiment, 93 synthesis step Step3.
Step2：Under nitrogen protection, in reactor be added pyrene quinone (3.48g, 15mmol), intermediate 214-1 (5.16g, 10mmol)、NH4HCO3(1.98g, 25mmol), ethyl alcohol 100mL reacts 12h at 100 DEG C, filters, detaches after reaction, use Ethyl alcohol washing is dried to obtain compound 214 (5.25g, 72%).
The synthesis of [embodiment 8] compound 235
Step1：Intermediate 235-1 is obtained with reference to the method for 1 compound of embodiment, 2 synthesis step Step4.
Step2：Intermediate 235-2 is obtained with reference to the method for 1 compound of embodiment, 2 synthesis step Step5.
Step3：Intermediate 235-3 is obtained with reference to the method for 1 compound of embodiment, 2 synthesis step Step6.
Step4：Under nitrogen protection, intermediate 235-3 (4.52g, 8.4mmol), Isosorbide-5-Nitrae-dibromobenzene are added in reaction vessel (2.17g, 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 235-4 later with silica gel column chromatography (3.62g, 76%).
Step5：In reactor be added intermediate 235-4 (5.67g, 10mmol), THF 50mL, after be cooled to -78 DEG C, add Enter n-Buli (0.64g, 10mmol), stir 1h, after be to slowly warm up to room temperature, DMF (1.83g, 25mmol) is added, is stirred at room temperature 3h is reacted, extracts organic phase afterwards, silicagel column is crossed and obtains intermediate 235-5 (3.25g, 63%).
Step6：Under nitrogen protection, in reactor be added phenanthrenequione (3.12g, 15mmol), intermediate 235-5 (5.16g, 10mmol), aniline (2.24g, 12mmol), ammonium acetate (0.75g, 100mmol), glacial acetic acid 100mL, back flow reaction are for 24 hours, cooling To room temperature, reactant is poured into methanol solution, stirred, detached, filtered, cleaned, being dried to obtain compound 235 (5.46g, 70%).
The values of FD-MS containing Benzofluorene 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=679.34 (C50H37N3=679.30)
Embodiment 2 M/z=644.32 (C47H36N2O=644.28)
Embodiment 3 M/z=703.35 (C52H37N3=703.30)
Embodiment 4 M/z=793.27 (C58H39N3O=793.31)
Embodiment 5 M/z=727.25 (C54H37N3=727.30)
Embodiment 6 M/z=728.18 (C53H36N4=728.29)
Embodiment 7 M/z=728.33 (C54H36N2O=728.28)
Embodiment 8 M/z=779.41 (C58H41N3=779.33)
[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 2 of embodiment 1.
[embodiment 10] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 53 of embodiment 2.
[embodiment 11] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 93 of embodiment 3.
[embodiment 12] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 135 of embodiment 4.
[embodiment 13] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 157 of embodiment 5.
[embodiment 14] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 173 of embodiment 6.
[embodiment 15] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 214 of embodiment 7.
[embodiment 16] device prepares embodiment：
The light emitting layer dopant matter DPAVBi of comparative example 1 is changed to the compound 235 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 Benzofluorene compound in organic luminescent device, especially as indigo plant The cut-in voltage of light object dopant, organic electro-luminance device reduces obviously, and luminous efficiency and service life are significantly increased, The present invention is luminous organic material of good performance containing Benzofluorene 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 Benzofluorene compound, which is characterized in that its general formula of molecular structure is as shown in chemical formula I：
Wherein, A is selected from substituted or unsubstituted C6~C60 aryl；X is selected from NR2, any one in O；R1、R2Independently selected from H, substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 aryl, substituted or unsubstituted C3~C60 are miscellaneous One kind in aryl；Ar1、Ar2Independently selected from substituted or unsubstituted C1~C30 alkyl, substituted or unsubstituted C6~C60 One kind in aryl, substituted or unsubstituted C3~C60 heteroaryls；L be selected from singly-bound, substituted or unsubstituted C6~C30 aryl, One kind in substituted or unsubstituted C3~C30 heteroaryls.
2. according to claim 1 a kind of containing Benzofluorene compound, which is characterized in that A is selected from substituted or unsubstituted C6 ~C30 aryl；X is selected from NR2, any one in O；R1、R2Independently selected from H, substituted or unsubstituted C1~C10 alkyl, take One kind in generation or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls；Ar1、Ar2Independently selected from Substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C30 aryl, substituted or unsubstituted C3~C30 heteroaryls One kind in base；L is in singly-bound, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted C3~C24 heteroaryls One kind.
3. according to claim 1 a kind of containing Benzofluorene compound, which is characterized in that A is selected from substituted or unsubstituted benzene Any one in base, substituted or unsubstituted naphthalene, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl.
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 Benzofluorene compound, which is characterized in that Ar1、Ar2Independently selected from substitution or Unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substitution or Unsubstituted triphenylene, substituted or unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted pheno Thiazinyl, substituted or unsubstituted phenoxazine thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substitution or Unsubstituted pyrenyl, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, takes substituted or unsubstituted ferrosin base Generation or unsubstituted pyridyl group, substituted or unsubstituted pyrazinyl, substituted or unsubstituted are rattled away at substituted or unsubstituted pyrimidine radicals Piperazine 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 Thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted hexichol And any one in furyl.
6. according to claim 1 a kind of containing Benzofluorene compound, which is characterized in that L is selected from singly-bound, substitution or unsubstituted Phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substitution or unsubstituted Pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substitution Or it is unsubstituted triazine radical, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted Triazolyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, takes substituted or unsubstituted thienyl Generation or unsubstituted benzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group In any one.
7. according to claim 1 a kind of containing Benzofluorene compound, which is characterized in that described selects containing Benzofluorene compound From any one in chemical constitution as follows：
8. a kind of organic luminescent device, which is characterized in that the organic luminescent device includes cathode, organic matter layer, anode successively； The organic matter layer is at least one layer of in the organic matter layer to contain claim 1~7 times between the cathode and anode Contain Benzofluorene compound described in one.
9. according to a kind of organic luminescent device described in claim 8, which is characterized in that the organic matter layer includes shining Layer, contain Benzofluorene compound containing claim 1~7 any one of them in luminescent layer.
CN201810533361.0A 2018-05-29 2018-05-29 One kind containing Benzofluorene compound and its organic luminescent device Withdrawn CN108774177A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019185061A1 (en) * 2018-03-29 2019-10-03 江苏三月光电科技有限公司 Bis(dimethylfluorene)-based compound, preparation method therefor and use thereof
CN112480011A (en) * 2020-12-04 2021-03-12 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, organic electroluminescent device, and electronic device
CN115583936A (en) * 2022-12-12 2023-01-10 烟台九目化学股份有限公司 Pyrene selenazole organic compound and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019185061A1 (en) * 2018-03-29 2019-10-03 江苏三月光电科技有限公司 Bis(dimethylfluorene)-based compound, preparation method therefor and use thereof
CN112480011A (en) * 2020-12-04 2021-03-12 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, organic electroluminescent device, and electronic device
CN115583936A (en) * 2022-12-12 2023-01-10 烟台九目化学股份有限公司 Pyrene selenazole organic compound and preparation method and application thereof
CN115583936B (en) * 2022-12-12 2023-02-28 烟台九目化学股份有限公司 Pyrene selenazole organic compound and preparation method and application thereof

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