CN108165264A - A kind of organic luminescent compounds and its preparation method and application - Google Patents

A kind of organic luminescent compounds and its preparation method and application Download PDF

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CN108165264A
CN108165264A CN201810141161.0A CN201810141161A CN108165264A CN 108165264 A CN108165264 A CN 108165264A CN 201810141161 A CN201810141161 A CN 201810141161A CN 108165264 A CN108165264 A CN 108165264A
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luminescent compounds
formula
organic luminescent
compound
organic
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尹恩心
林文晶
彭勃
马晓宇
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Shanghai Sheng Xi Photoelectric Technology Co Ltd
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Shanghai Sheng Xi Photoelectric Technology Co Ltd
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Abstract

The present invention relates to a kind of organic luminescent compounds and its preparation method and applications, belong to organic electroluminescent compounds field.Organic luminescent compounds provided by the invention, by selecting specific mother nucleus structure and substituent group so that after obtained compound is applied to organic electroluminescence device, the luminous efficiency of device improves, and service life is long.The preparation method of organic luminescent compounds provided by the invention, preparation method is simple, is easy to industrialized production.

Description

A kind of organic luminescent compounds and its preparation method and application
Technical field
The present invention relates to organic electroluminescent compounds fields, and in particular to a kind of organic luminescent compounds and its preparation method and Using.
Background technology
Organic electroluminescence device (organic electroluminescence device:OLED it is) in organic light emission It is subject to voltage in material, electric energy is made to be converted into a kind of device of luminous energy, usual structure is with anode (anode), cathode (cathode) the organic matter layer composition between the two poles of the earth.Organic matter layer in organic electroluminescence device can be injected by hole Layer, hole transmission layer, electron blocking layers, luminescent layer (including material of main part and dopant material), electron buffer layer, hole blocking The formation such as layer, electron transfer layer, electron injecting layer.It can be divided into according to function difference as the material in organic matter layer, hole note Enter material, hole mobile material, electron-block material, luminescent material, electronics padded coaming, hole blocking material, electron-transport Material, electron injection material etc..After such organic electroluminescence device is subject to voltage, hole is injected from anode, is injected from cathode Electronics is compounded to form the exciton of high-energy by hole and electronics, gives off energy, transfer energy to organic hair to luminescent layer Stimulative substance molecule, making it, excited molecule returns to ground state from excitation state again from ground state transition to excitation state, radiation transistion and generate hair Optical phenomenon.
Wherein electron transport material be by electronics from cathode smooth delivery of power to luminescent layer, and inhibit in luminescent layer be not associated with Hole movement come increase hole and electronics in luminescent layer in conjunction with chance, the outstanding material of general electron affinity is It may be used as electron transport material.Similar Alq3 has the metal-organic complex of lighting function, because electronics locomotivity is outstanding, Usually it is used as electron transport material.But oriented other layer of Alq3 is mobile and has reduction color purity etc. to ask in blue-light device Topic.It it requires that a kind of Novel electronic transmission material emerges, there is no the above problems, have high electron affinity, and be used in During organic electroluminescence device, quick electronics mobility shows high luminous efficiency.
Invention content
The object of the present invention is to provide a kind of organic luminescent compounds and its preparation method and application, compound provided by the invention It is applied to organic electroluminescence device as electron transport material so that not only luminous efficiency is high, but also uses for obtained device Long lifespan.
To achieve these goals, technical scheme of the present invention is specific as follows：
A kind of organic luminescent compounds, structural formula are as follows：
In formula：
R1For aryl；
R2Structure it is as follows：
Wherein, X is nitrogen, oxygen or sulphur；R2By " * " position indicated and on the phenyl ring being attached thereto；
R3For hydrogen；
Ar1For any one in having structure：
Wherein X is C or N, at least one is N,For with N connecting portions；
Ar2And Ar3It is each independently selected from hydrogen, substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocycle Base.
In the above-mentioned technical solutions, R1For phenyl, Ar2And Ar3It is each independently selected from hydrogen, carbon atom number is taking for 6-12 Generation or unsubstituted phenyl or the substituted or unsubstituted aromatic heterocyclic radical that carbon atom number is 12.
In the above-mentioned technical solutions, R1For phenyl, Ar2And Ar3It is each independently selected from hydrogen, phenyl, xenyl or dibenzo Thienyl.
In the above-mentioned technical solutions, the organic luminescent compounds are any one in following concrete structure：
A kind of preparation method of organic luminescent compounds, includes the following steps：
By the compound of formula (II) structure and the compound hybrid reaction of formula (III) structure, structure shown in formula (I) is obtained Organic luminescent compounds；
According to the present invention, by the compound of formula (II) structure and the compound hybrid reaction of formula (III) structure, formula is obtained (I) compound of structure, in of the invention, R in the compound of formula (II) structure1、R2And R3Range of choice and aforesaid compound In restriction it is identical；Ar in the compound of formula (III) structure1、Ar2And Ar3The selection of substituent group is also limited with aforesaid compound Fixed identical, the present invention does not have the condition of the reaction particular/special requirement, and those skilled in the art can select according to existing reaction Select suitable reaction condition.In addition, the present invention does not have the source of the compound and the compound of formula (III) structure of formula (II) structure There is particular determination, be made by preparation method well known in the art.
The present invention also provides a kind of organic luminescent compounds of the present invention to have as electron transport layer materials in preparation Application in organic electroluminescence devices.
The beneficial effects of the invention are as follows：
Organic luminescent compounds provided by the invention, by selecting specific mother nucleus structure and substituent R1、R2And R3, And Ar1、Ar2And Ar3So that after obtained compound is applied to organic electroluminescence device, the luminous efficiency of device improves, and And service life is long.
The preparation method of organic luminescent compounds provided by the invention, preparation method is simple, is easy to industrialized production.
Specific embodiment
The present invention provides a kind of organic luminescent compounds, and structural formula is as follows：
In formula：
R1For aryl；
R2Structure it is as follows：
Wherein, X is nitrogen, oxygen or sulphur；R2By " * " position indicated and on the phenyl ring being attached thereto；
R3For hydrogen；
Ar1For any one in having structure：
Wherein X is C or N, at least one is N,For with N connecting portions；
Ar2And Ar3It is each independently selected from hydrogen, substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocycle Base.
Preferably, R1For phenyl, Ar2And Ar3Be each independently selected from hydrogen, carbon atom number be 6-12 substitution or do not take The phenyl or carbon atom number in generation are 12 substituted or unsubstituted aromatic heterocyclic radical.
It is still preferred that R1For phenyl, Ar2And Ar3It is each independently selected from hydrogen, phenyl, xenyl or dibenzothiophenes Base.
Most preferably described organic luminescent compounds are any one in following concrete structure：
The present invention also provides a kind of preparation methods of organic luminescent compounds, include the following steps：
By the compound of formula (II) structure and the compound hybrid reaction of formula (III) structure, structure shown in formula (I) is obtained Organic luminescent compounds；
According to the present invention, by the compound of formula (II) structure and the compound hybrid reaction of formula (III) structure, formula is obtained (I) compound of structure, in of the invention, R in the compound of formula (II) structure1、R2And R3Range of choice and aforesaid compound In restriction it is identical；Ar in the compound of formula (III) structure1、Ar2And Ar3The selection of substituent group is also limited with aforesaid compound Fixed identical, the present invention does not have the condition of the reaction particular/special requirement, and those skilled in the art can select according to existing reaction Select suitable reaction condition.In addition, the present invention does not have the source of the compound and the compound of formula (III) structure of formula (II) structure There is particular determination, be made by preparation method well known in the art.
The present invention also provides a kind of organic luminescent compounds of the present invention to have as electron transport layer materials in preparation Application in organic electroluminescence devices.
The present invention is clearly and completely described below in conjunction with embodiment, it is clear that described embodiment is only Part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art All other embodiments obtained without making creative work shall fall within the protection scope of the present invention.
The compound of formula (III) structure is preferably the substance such as lower structure：
The synthesis of first intermediate
Sequentially add reactant 1-1 (19.48g, 89mmol) into 1L round-bottomed flasks, connection boric acid pinacol ester (27g, 106mmol), two (triphenylphosphine) palladium chloride (3.1g, 4.45mmol), potassium acetate (KOAc) (22g, 222mmol) and Isosorbide-5-Nitrae- After dioxane (445mL) heating stirring to back flow reaction 3 hours, mixture dichloromethane and deionized water are extracted, two Chloromethanes layer filters after being dried with anhydrous magnesium sulfate, after obtained solid is dissolved with chloroform, is obtained by column chromatography for separation Intermediate 1-1 (13.08g, 60%).
The reactant and yield table of 1 first intermediate of table
According to above-mentioned preparation method, reactant 1-1 is substituted for reactant 1-2 or reactant 1-3, with same molar ratio Intermediate 1-2 and intermediate 1-3 is prepared.
The synthesis of second intermediate and third intermediate
0.10mol intermediate 1-1,0.10mol diiodoanilines and tetra-triphenylphosphine palladium 7.0g are added in reaction bulb, added Enter toluene 600mL, aqueous sodium carbonate (2N, 250mL), under the protection of nitrogen 90 DEG C of oil bath reacted, overnight.It will reaction Rear system cooling, is spin-dried for toluene at liquid separation, and obtained residue is entirely molten with dichloromethane, adds the petroleum ether of equivalent, mistake Silica gel funnel, and use dichloromethane：Petroleum ether=1：2 (volume ratios) are rinsed, and until no product point flows out, collect filtrate, and revolve Dry solvent obtains intermediate 2-1 (0.081mol, y=81%).
Under condition of nitrogen gas, 0.081mol intermediates 2-1, hydrochloric acid (10mL), acetic acid are added in 500mL two-mouth bottles It is refluxed 24 hours after (350mL), crosses filter solid after the cooling of reaction solution room temperature, washed several times with methanol, utilize hexane The isolated intermediate 3-1 (11.27g, y=50%) of silicagel column.
Table 2
According to above-mentioned preparation method, reactant is substituted for the reactant of serial number 2~14 and corresponding intermediate in table 2, Intermediate 2-2 to intermediate 2-14 and intermediate 3-2 is prepared to intermediate 3-14 with same molar ratio.
The synthesis of 4th intermediate
Sequentially add intermediate 3-1 (8.4g, 20.6mmol) into 500mL round-bottomed flasks, fluorobenzene (2.38g, 24.8mmol), palladium (232mg, 1.0mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl (850mg, 2.0mmol), sodium tert-butoxide (5g, 51.6mmol) and ortho-xylene 200mL are stirred 2 hours, reaction mixture second in 180 DEG C Acetoacetic ester/water is post-processed, after removing residual moisture with magnesium sulfate, vacuum distillation, and crude product dichloromethane：N-hexane carries out Column chromatography for separation obtains intermediate 4-1 (4.45g, 55%).
Table 3
According to above-mentioned preparation method, third intermediate is replaced with into the corresponding intermediate described in table 3, uses same molar Than intermediate 4-2 is prepared to intermediate 4-5.
The synthesis of 5th intermediate：
Non- that alkene -1- ketone (20g, 111mmol) of 1H- are added in into reaction bulb, are dissolved with tetrahydrofuran (554mL) after 0 DEG C phenyl-magnesium-bromide (36.9mL) is slowly added dropwise, and be stirred at room temperature 24 hours, after reaction, is extracted with ethyl acetate organic Layer, obtained organic layer remove residual moisture with anhydrous magnesium sulfate, 1- phenyl -1H- benzo naphthalene -1- alcohol are obtained using column chromatography for separation (21.5g, 75%).
Into reaction bulb add in 1- phenyl -1H- benzo naphthalene -1- alcohol (17.5g, 67.7mmol) and bromobenzene (10.6, 67.7mmol), it is dissolved with dichloromethane (450mL), the methanesulfonic acid solution (0.04mL, 1.35mmol) of phosphorus pentoxide will be subject to It is added dropwise in above-mentioned reaction solution, stirs ten minutes, after reaction, add in sodium bicarbonate solution, extracted with dichloromethane organic Layer.Residual moisture is removed with anhydrous magnesium sulfate again, 1- (4- bromophenyls) -1- phenyl -1H- benzo naphthalenes are obtained using column chromatography for separation (24.2g, 90%).
1- (4- bromophenyls) -1- phenyl -1H- benzos naphthalenes (35.4g, 89mmol) are sequentially added into 1L round-bottomed flasks, are joined Boric acid pinacol ester (27g, 106mmol), two (triphenylphosphine) palladium chlorides (3.1g, 4.45mmol), potassium acetate (KOAc) (22g, 222mmol) and Isosorbide-5-Nitrae-dioxane (445mL) heating stirring to flowing back, after 3 hours by mixture dichloromethane and Deionized water extracts, and dichloromethane layer is filtered after being dried with anhydrous magnesium sulfate, after obtained solid is dissolved with chloroform, passed through Column chromatography for separation obtains the 5th intermediate (23.73g, 60%).
The synthesis of 6th intermediate：
The 5th intermediate of 78mmol intermediates 4-1,93mmol, tetrakis triphenylphosphine palladium are sequentially added into 2L round-bottomed flasks 3.1mmol, sodium carbonate 195mmol, toluene 400mL, ethyl alcohol 50mL and water 100mL dissolving are stirred overnight after 130 DEG C, and reaction is mixed Close object ethyl acetate/H2O processing, then be evaporated under reduced pressure after being dried with anhydrous magnesium sulfate, crude product dichloromethane：N-hexane carries out Column chromatography for separation obtains intermediate 6-1, (60.84mmol, 78%).
57.8mmol intermediate 6-1, triethyl phosphite 200mL and o-dichlorohenzene are sequentially added into 1L round-bottomed flasks 200mL is stirred 2 hours in 150 DEG C, and reaction mixture rotates to obtain solid, crude product dichloromethane：N-hexane carries out column chromatography Isolated intermediate 7-1 (45.66mmol, 79%).
Table 4
According to above-mentioned preparation method, intermediate 4-1 is replaced with into the corresponding intermediate described in table 4, uses same molar Than intermediate 7-2 is prepared to intermediate 7-14.
The synthesis of target compound shown in formula 1- formulas 16
Sequentially add 20.6mmol intermediate 7-1 into 500mL round-bottomed flasks, formula (III) compound represented in table 5 24.8mmol, palladium 1.0mmol, 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl 2.0mmol, sodium tert-butoxide 51.6mmol and ortho-xylene 200mL is stirred 2 hours in 180 DEG C, and reaction mixture is post-processed with ethyl acetate/water, is used After magnesium sulfate removes residual moisture, vacuum distillation, crude product dichloromethane：N-hexane carries out column chromatography for separation and obtains shown in formula 1 Compound (11.54mmol, 56%), labeled as P1.
Table 5
According to above-mentioned preparation method, intermediate 7-1 and formula (III) compound represented are replaced with respectively described in table 5 Corresponding intermediate and respective compound, 16 compound represented of formula 2- formulas is prepared with same molar ratio, marks respectively For P2-P16.
The above-mentioned mass spectrometric data of compound P1-P16 being prepared is shown in Table 6.
Table 6
Serial number FD-MS Serial number FD-MS
P1 M/z=879.34 (C54H41N5=880.94) P 2 M/z=803.30 (C56H37N5=803.95)
P 3 M/z=802.31 (C59H38N4=802.96) P 4 M/z=801.31 (C60H39N3=801.97)
P 5 M/z=803.30 (C58H57N5=803.95) P 6 M/z=878.34 (C65H42N4=879.06)
P 7 M/z=820.27 (C58H36N4S=821.00) P 8 M/z=925.26 (C65H39N3S2=926.16)
P 9 M/z=896.30 (C64H40N4S=897.09) P 10 M/z=743.24 (C53H33N3S=743.91)
P 11 M/z=773.20 (C63H31N3S2=773.96) P 12 M/z=803.29 (C59H37N3O=803.29)
P 13 M/z=833.25 (C59H35N3OS=833.99) P 14 M/z=804.29 (C58H36N4O=804.93)
P 15 M/z=727.26 (C53H33N3O=727.85) P 16 M/z=757.22 (C53H31N3OS=757.90)
The preparation of organic electroluminescence device
[experimental example 1-16] green organic electrofluorescence device (electron transfer layer)
First, vacuum evaporation thickness is the 4,4' of 60nm to the indium tin oxide layer (anode) formed in glass substrate above, 4 "-three [2- naphthylphenyls amino] triphenylamines (hereinafter referred to as 2-TNATA) form hole injection layer, are noted in the hole of formation Enter the N that vacuum evaporation thickness above layer is 60nm, N'- diphenyl-N, N'- (1- naphthalenes) -1,1'- biphenyl -4,4'- diamines (with It is referred to as NPD down) form hole transmission layer.Then, vacuum evaporation thickness is 30nm on above-mentioned hole transmission layer, with Based on 4,4'- bis- (9- carbazoles) biphenyl (hereinafter referred to as CBP), close iridium using three (2- phenylpyridines) is as the mixture adulterated Luminescent layer, material of main part and dopant material weight ratio are 95:5.And then, vacuum evaporation thickness is on above-mentioned luminescent layer Bis- (2- methyl -8-hydroxyquinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyls) aluminium (hereinafter referred to as BAlq) of 10nm forms sky Cave barrier layer.It is arbitrary in the compound of the present invention P1~P16 of the vacuum evaporation thickness for 40nm above above-mentioned hole blocking layers One formation electron transfer layer.Then, fluorination of the evaporation thickness for 0.2nm alkali halides on above-mentioned electron transfer layer Lithium forms electron injecting layer.Then evaporation thickness is that the aluminium of 150nm forms cathode, and organic electroluminescence is completed with this The preparation of part.
Comparative example (1)
Other than electron transfer layer substance replaces the compound of the present invention with comparative compound 1, other all with it is above-mentioned The same method of experimental example prepares organic electroluminescence device.
<Comparative compound 1>Alq3
Other than electron transfer layer substance replaces the compound of the present invention with comparative compound 2, other all with it is above-mentioned The same method of experimental example prepares organic electroluminescence device.
<Comparative compound 2>
Other than electron transfer layer substance replaces the compound of the present invention with comparative compound 3, other all with it is above-mentioned The same method of experimental example prepares organic electroluminescence device.
<Comparative compound 3>
Forward dc bias voltage is subject to the organic electroluminescence device of above-mentioned preparation, utilizes Photo Resea rch The PR-650 photometric devices of company measure electroluminescence characters, and in 5000cd/m2Benchmark gray scale under utilize The biometrics device of McScience companies manufacture determines the service life of T95, and measurement result is documented in table 7.
Table 7
Can see from above-mentioned table 7, by the use of the compound of the present invention as organic electroluminescence device (OLED) in electronics Transport layer with comparative compound 1 as the electron transfer layer in organic electroluminescence device (OLED), embodies following advantage, Lower driving voltage, high efficiency and the high service life.
Then, by the use of the compound of the present invention as the organic electroluminescence device (OLED) of electron transfer layer and comparison Object 2, comparative compound 3 is closed to compare as the organic electroluminescence device of electron transfer layer, it is known that, when with the present invention In compound when, be all significantly improved in luminous efficiency and on the service life.This can illustrate, the compound phase in the present invention Compared with comparative compound 2 and comparative compound 3, the charge balance of hole and electronics is preferably maintained.
The currently preferred specific embodiment of above description, It should be understood by those skilled in the art that the present invention is not by upper The limitation of embodiment is stated, the present invention also has various changes without departing from the spirit and scope of the present invention, this A little changes and improvements are both fallen in the scope of protection of present invention.The claimed scope of the invention is by appended claims And its equivalent defines.

Claims (6)

1. a kind of organic luminescent compounds, which is characterized in that its structural formula is as follows：
In formula：
R1For aryl；
R2Structure it is as follows：
Wherein, X is nitrogen, oxygen or sulphur；R2By " * " position indicated and on the phenyl ring being attached thereto；
R3For hydrogen；
Ar1For any one in having structure：
Wherein X is C or N, at least one is N,For with N connecting portions；
Ar2And Ar3It is each independently selected from hydrogen, substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical.
2. organic luminescent compounds according to claim 1, which is characterized in that R1For phenyl, Ar2And Ar3Each independently Selected from hydrogen, carbon atom number be 6-12 substituted or unsubstituted phenyl or carbon atom number be 12 substituted or unsubstituted aromatics Heterocycle.
3. organic luminescent compounds according to claim 1, which is characterized in that R1For phenyl, Ar2And Ar3Each independently Selected from hydrogen, phenyl, xenyl or dibenzothiophene.
4. organic luminescent compounds according to claim 1, which is characterized in that the organic luminescent compounds are following tool Any one in body structure：
5. the preparation method of organic luminescent compounds described in claim 1, which is characterized in that include the following steps：
By the compound of formula (II) structure and the compound hybrid reaction of formula (III) structure, the organic of structure shown in formula (I) is obtained Luminophor；
In formula：
R1For aryl；
R2Structure it is as follows：
Wherein, X is nitrogen, oxygen or sulphur；R2By " * " position indicated and on the phenyl ring being attached thereto；
R3For hydrogen；
Ar1For any one in having structure：
Wherein X is C or N, at least one is N,For with N connecting portions；
Ar2And Ar3It is each independently selected from hydrogen, substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical.
6. organic luminescent compounds described in claim 1 are as electron transport layer materials in organic electroluminescence device is prepared Application.
CN201810141161.0A 2018-02-11 2018-02-11 A kind of organic luminescent compounds and its preparation method and application Pending CN108165264A (en)

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