CN108003143A - A kind of organic luminescent compounds and preparation method thereof and organic electroluminescence device - Google Patents

A kind of organic luminescent compounds and preparation method thereof and organic electroluminescence device Download PDF

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CN108003143A
CN108003143A CN201711261638.0A CN201711261638A CN108003143A CN 108003143 A CN108003143 A CN 108003143A CN 201711261638 A CN201711261638 A CN 201711261638A CN 108003143 A CN108003143 A CN 108003143A
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luminescent compounds
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王进政
崔明
王钊
刘成凯
刘志远
金福荣
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Jilin Optical and Electronic Materials Co Ltd
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Abstract

The present invention relates to a kind of organic luminescent compounds and preparation method thereof and organic electroluminescence device, it is related to luminescent material technical field.It is provided by the invention with it is more appropriate it is chromaticity coordinates, purity is high, the organic luminescent compounds of outstanding skeleton are as organic electroluminescence device electron transport layer materials, compared with other electron transport layer materials, the organic electroluminescence device prepared by the use of organic luminescent compounds provided by the invention as electron transport layer materials, its luminous efficiency significantly improves, the service life is obviously improved.The preparation method of organic luminescent compounds provided by the invention, raw material are easy to get, and technique is simple, are suitable for industrialized production.

Description

A kind of organic luminescent compounds and preparation method thereof and organic electroluminescence device
Technical field
The present invention relates to luminous organic material field, and in particular to a kind of organic luminescent compounds and preparation method thereof and has Organic electroluminescence devices.
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 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 can be by hole injection layer, hole transmission layer, electronics resistance Tomography, luminescent layer (including material of main part and dopant material), electron buffer layer, hole blocking layers, electron transfer layer, electron injection Layer etc. is formed.It can be divided into according to function difference as the material in organic matter layer：Hole-injecting material, hole mobile material, electricity Sub- occluding material, luminescent material, electronics padded coaming, hole blocking material, electron transport material, electron injection material etc..This After kind of organic electroluminescence device is subject to voltage, inject hole from anode, inject electronics to luminescent layer from cathode, by hole with Electronics is compounded to form the exciton of high-energy, gives off energy, and transfers energy to the molecule of organic luminescent substance, makes it from ground state Transit to excitation state, excited molecule returns to ground state from excitation state again, radiation transistion and produce luminescence phenomenon.
In organic electroluminescence device, electron transport material be by electronics from cathode smooth delivery of power to luminescent layer, and suppress The movement in the hole being not associated with luminescent layer increase hole and electronics in luminescent layer in conjunction with chance, general electronics parent Outstanding material just may be used as electron transport material with property.Similar Alq3 has the metal-organic complex of lighting function, because Electronics locomotivity is outstanding, usually as electron transport material.But other oriented layers of Alq3 are mobile and in blue-light device There is the problems such as reducing color purity.It it requires that a kind of Novel electronic transmission material emerges, there is no the above problem, has high Electron affinity, and when being used in organic electroluminescence device, quick electronics mobility show high luminous efficiency.
The content of the invention
The invention solves technical problem of the prior art, there is provided a kind of organic luminescent compounds of new structure and its Preparation method and organic electroluminescence device, the organic luminescent compounds are used as organic electroluminescent prepared by electron transport material Luminous efficiency, stability and the service life of device are significantly increased.
In order to solve the above-mentioned technical problem, technical scheme is specific as follows：
A kind of organic luminescent compounds, its chemical structural formula are as shown in Equation 1：
In formula：X is O or S；
Ar1For substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical；
Ar is hydrogen or benzene；
In formula dotted line indicate position can and upper phenyl.
In the above-mentioned technical solutions, the organic luminescent compounds are any one in following structures：
In the above-mentioned technical solutions, Ar1The substituted or unsubstituted phenyl or carbon number for being 6-16 for carbon number be The substituted or unsubstituted aromatic heterocyclic radical of 5-11.
In the above-mentioned technical solutions, Ar1The substituted or unsubstituted phenyl or carbon number for being 11-16 for carbon number For the substituted or unsubstituted aromatic heterocyclic radical of 6-10.
In the above-mentioned technical solutions, Ar1The substituted or unsubstituted phenyl or carbon number for being 11 for carbon number are 7 Substituted or unsubstituted aromatic heterocyclic radical.
In the above-mentioned technical solutions, Ar1For pyridine radicals, picolyl, dimethyl pyrazole piperidinyl, methylpyrimidine base, diformazan Yl pyrimidines base, 4- pyridinylphenyls, 4- (3- methylisoquinoliniums base) phenyl, 2,3- dimethyl -1,4- quinoxalinyls, 2- methyl are different Quinolyl or 2- methyl bipyridyls.
In the above-mentioned technical solutions, the organic luminescent compounds are any one of following shown structures：
A kind of preparation method of organic luminescent compounds, comprises the following steps：
Chloro- [1,1'- the biphenyl] -3- formaldehyde of step 1, the 5- for substituting bromine, benzamidine hydrochloride, K3PO4It is placed in dimethyl sulfoxide (DMSO) In, heat the mixture to 90 DEG C reaction 1 it is small when, after the completion of reaction, water is added into reaction mixture, mixture is filtered To faint yellow solid, chloro- 5, the 6- dicyano p-benzoquinones of 2,3- bis- are added into the solution, are stirred at room temperature 10 minutes, reacted After the completion of, filter, vacuum distillation, for gained crude product by silica gel chromatography, the hexane using 0-10% ethyl acetate is molten Liquid obtains intermediate 1 as eluant, eluent；
Step 2, weigh intermediate 1, compoundPotassium carbonate and tetra-triphenylphosphine palladium, and will Tetrahydrofuran and H2O is added thereto, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4It is dry And be evaporated under reduced pressure, crude product is recrystallized, obtains intermediate
Step 3, by intermediateDouble (pinacol) two boron, potassium acetate, double (dibenzylidenes Acetone) palladium, tricyclohexyl phosphine, be placed in dioxanes and flow back 12 it is small when, after the completion of reaction, mixture is cooled to room temperature, mistake Filter out and desalt, gained liquid pressure-reducing is distilled, obtains dark brown solid, is recrystallized to give intermediate
Step 4, by intermediateAr1- Br, tetra-triphenylphosphine palladium and potassium carbonate are molten In tetrahydrofuran and H2In O, when reflux 12 is small, after the completion of reaction, reaction mixture is cooled to room temperature, filters consolidating for precipitation Body, is dissolved in CHCl by obtained solid3In, use MgSO4It is dry, filtered by diatomite, recrystallize, obtain formula 1Shown compound；
Its synthetic route is as follows：
In formula：X is O or S；Ar1For substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical；Ar is Hydrogen or benzene；In formula dotted line indicate position can and upper phenyl.
A kind of organic electroluminescence device, its electron transport layer materials are the organic luminescent compounds shown in formula 1.
The organic luminescent compounds can be applied to organic photovoltaic cell, Electronic Paper, Organophotoreceptor, organic transistor Or ink-jet printing material.
The beneficial effects of the invention are as follows：
It is provided by the invention with it is more appropriate it is chromaticity coordinates, purity is high, the organic luminescent compounds of outstanding skeleton It is as organic electroluminescence device electron transport layer materials, compared with other electron transport layer materials, use is provided by the invention The organic electroluminescence device that organic luminescent compounds are prepared as electron transport layer materials, its luminous efficiency significantly improves, the longevity Life is obviously improved.
The preparation method of organic luminescent compounds provided by the invention, raw material are easy to get, and technique is simple, are suitable for industrial metaplasia Production.
Embodiment：
A kind of organic luminescent compounds provided by the invention, its chemical structural formula are as shown in Equation 1：
In formula：X is O or S；Ar1For substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical；Ar is Hydrogen or benzene；In formula dotted line indicate position can and upper phenyl.
It is preferred that the organic luminescent compounds are any one in following structures：
In structure above, preferably Ar1The substituted or unsubstituted phenyl or carbon number for being 6-16 for carbon number For the substituted or unsubstituted aromatic heterocyclic radical of 5-11.Further preferred Ar1The substitution or unsubstituted for being 11-16 for carbon number Phenyl or carbon number be 6-10 substituted or unsubstituted aromatic heterocyclic radical.Further preferably Ar1It is 11 to take for carbon number Generation or the substituted or unsubstituted aromatic heterocyclic radical that unsubstituted phenyl or carbon number are 7.More preferably Ar1For pyridine radicals, first Yl pyridines base, dimethyl pyrazole piperidinyl, methylpyrimidine base, dimethyl pyrimidine base, 4- pyridinylphenyls, 4- (3- methylisoquinoliniums base) Phenyl, 2,3- dimethyl -1,4- quinoxalinyls, 2- methylisoquinoliniums base or 2- methyl bipyridyls.
The most preferably described organic luminescent compounds are any one of following shown structures：
The present invention also puies forward a kind of preparation method of organic luminescent compounds, comprises the following steps：
Chloro- [1,1'- the biphenyl] -3- formaldehyde of step 1, the 5- for substituting bromine, benzamidine hydrochloride, K3PO4It is placed in dimethyl sulfoxide (DMSO) In, heat the mixture to 90 DEG C reaction 1 it is small when, after the completion of reaction, water is added into reaction mixture, mixture is filtered To faint yellow solid, chloro- 5, the 6- dicyano p-benzoquinones of 2,3- bis- are added into the solution, are stirred at room temperature 10 minutes, reacted After the completion of, filter, vacuum distillation, for gained crude product by silica gel chromatography, the hexane using 0-10% ethyl acetate is molten Liquid obtains intermediate 1 as eluant, eluent；
Step 2, weigh intermediate 1, compoundPotassium carbonate and tetra-triphenylphosphine palladium, and will Tetrahydrofuran and H2O is added thereto, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4It is dry And be evaporated under reduced pressure, crude product is recrystallized, obtains intermediate
Step 3, by intermediateDouble (pinacol) two boron, potassium acetate, double (dibenzylidenes Acetone) palladium, tricyclohexyl phosphine, be placed in dioxanes and flow back 12 it is small when, after the completion of reaction, mixture is cooled to room temperature, mistake Filter out and desalt, gained liquid pressure-reducing is distilled, obtains dark brown solid, is recrystallized to give intermediate
Step 4, by intermediateAr1- Br, tetra-triphenylphosphine palladium and potassium carbonate are molten In tetrahydrofuran and H2In O, when reflux 12 is small, after the completion of reaction, reaction mixture is cooled to room temperature, filters consolidating for precipitation Body, is dissolved in CHCl by obtained solid3In, use MgSO4It is dry, filtered by diatomite, recrystallize, obtain formula 1Shown compound；
Its synthetic route is as follows：
In formula：X is O or S；Ar1For substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical；Ar is Hydrogen or benzene；In formula dotted line indicate position can and upper phenyl.
The present invention also provides a kind of organic electroluminescence device, its electron transport layer materials is the organic light emission shown in formula 1 Compound.
By the bromo- 5- chlorobenzaldehydes (118.3mmol) of 3-, (3- bromophenyls) boric acid (118.3mmol), potassium carbonate (354.9mmol), tetra-triphenylphosphine palladium (2mol%) are put into round-bottomed flask, and by tetrahydrofuran (THF) (500mL) and H2O (250mL) pour into wherein, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4Dry and subtract Pressure distillation.Crude product is recrystallized, obtains chloro- [1,1'- the biphenyl] -3- formaldehyde (70.98mmol, yield 60%) of the bromo- 5- of 3'-.
The synthesis of 2- (chloro- [1,1'- the biphenyl] -3- bases of the bromo- 5- of 3'-) -4,6- diphenyl -1,3,5- triazines：
By chloro- [1,1'- the biphenyl] -3- formaldehyde (136.7mmol) of the bromo- 5- of 3'-, benzamidine hydrochloride (273.4mmol), K3PO4 (273.4mmol) is placed in dimethyl sulfoxide (DMSO) (DMSO), heat the mixture to 90 DEG C reaction 1 it is small when.After the completion of reaction, to anti- Answer and water is added in mixture, faint yellow solid is obtained by filtration, then chloro- 5, the 6- dicyanos pair of 2,3- bis- are added into the solution Benzoquinones (DDQ) (136.7mmol), is stirred at room temperature 10 minutes.After the completion of reaction, filter, vacuum distillation.Gained crude product leads to Silica gel chromatography is crossed, using the hexane solution of 0-10% ethyl acetate as eluant, eluent, obtains intermediate 1-1 (118.9mmol, yield 87%), theoretical value 497.03, measured value 497.06.
By raw materialIt is substituted forAccording to the preparation of intermediate 1-1 Method, prepares intermediate 1-2With intermediate 1-3
The synthesis of [synthesis example 1] compound 001
By intermediate 1-1 (118.3mmol), benzo [b] naphtho- [2,3-d] furans -2- ylboronic acids (118.3mmol), carbon Sour potassium (354.9mmol), tetra-triphenylphosphine palladium (2mol%) are put into round-bottomed flask, and by tetrahydrofuran (THF) (500mL) and H2O (250mL) pour into wherein, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4Drying is simultaneously Vacuum distillation.Crude product is recrystallized, obtains intermediate 2-1 (107.65mmol, yield 91%), theoretical value 635.18, is surveyed Value is 635.17.
Intermediate 2-1 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol) is double (dibenzalacetone) palladium (3mol%), tricyclohexyl phosphine (6mol%), be placed in dioxanes (500mL) and flow back 12 it is small when. After the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, gained liquid pressure-reducing is distilled, obtains dark brown solid, will It is recrystallized to give intermediate 3-1 (96.19mmol, yield 82%), theoretical value 727.30, measured value 727.25.
By intermediate 3-1 (22.1mmol), 3- bromopyridines (22.1mmol), tetra-triphenylphosphine palladium (0.76g, 3mol%) and Potassium carbonate (6.11g, 44.2mmol) is dissolved in tetrahydrofuran THF (110mL) and H2In O (55mL), when reflux 12 is small.Reaction is completed Afterwards, reaction mixture is cooled to room temperature, filtered.Obtained solid is dissolved in CHCl3In, use MgSO4It is dry, pass through diatomite mistake Filter, recrystallization, obtains compound 001 (13.70mmol, yield 62%), theoretical value 678.24, measured value 678.20.
The synthesis of [synthesis example 2] compound 002
By intermediate 1-2 (118.3mmol), phenanthro- [9,10-b] benzofuran -12- ylboronic acids (118.3mmol), carbonic acid Potassium (354.9mmol), tetra-triphenylphosphine palladium (2mol%) are put into round-bottomed flask, and by tetrahydrofuran (THF) (500mL) and H2O (250mL) pour into wherein, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4Drying is simultaneously Vacuum distillation, crude product is recrystallized, and obtains intermediate 2-2 (107.65mmol, yield 91%), theoretical value 685.19, is surveyed Value is 685.25.
Intermediate 2-2 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol) is double (dibenzalacetone) palladium (3mol%), tricyclohexyl phosphine (6mol%), be placed in dioxanes (500mL) and flow back 12 it is small when. After the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, gained liquid pressure-reducing is distilled, obtains dark brown solid, will It is recrystallized to give intermediate 3-2 (96.19mmol, yield 82%), theoretical value 777.32, measured value 777.36.
By intermediate 3-2 (22.1mmol), 3- bromopyridines (22.1mmol), tetra-triphenylphosphine palladium (0.76g, 3mol%) and Potassium carbonate (6.11g, 44.2mmol) is dissolved in tetrahydrofuran THF (110mL) and H2In O (55mL), when reflux 12 is small.Reaction is completed Afterwards, reaction mixture is cooled to room temperature, filtered.Obtained solid is dissolved in CHCl3In, use MgSO4It is dry, pass through diatomite mistake Filter, recrystallization, obtains compound 002 (13.70mmol, yield 62%), theoretical value 702.24, measured value 702.28.
The synthesis of [synthesis example 3] compound 003
By intermediate 1-3 (118.3mmol), benzo [b] phenanthro- [9,10-d] thiophene -12- ylboronic acids (118.3mmol), Potassium carbonate (354.9mmol), tetra-triphenylphosphine palladium (2mol%) are put into round-bottomed flask, and by tetrahydrofuran (THF) (500mL) And H2O (250mL) pour into wherein, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4It is dry And be evaporated under reduced pressure, crude product is recrystallized, obtains intermediate 2-2 (107.65mmol, yield 91%), theoretical value 701.17, Measured value is 701.20.
Intermediate 2-3 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol) is double (dibenzalacetone) palladium (3mol%), tricyclohexyl phosphine (6mol%), be placed in dioxanes (500mL) and flow back 12 it is small when, After the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, gained liquid pressure-reducing is distilled, obtains dark brown solid, will It is recrystallized to give intermediate 3-3 (96.19mmol, yield 82%), theoretical value 793.29, measured value 793.35.
By intermediate 3-3 (22.1mmol), 4- bromopyridines (22.1mmol), tetra-triphenylphosphine palladium (0.76g, 3mol%) and Potassium carbonate (6.11g, 44.2mmol) is dissolved in tetrahydrofuran THF (110mL) and H2In O (55mL), when reflux 12 is small.Reaction is completed Afterwards, reaction mixture is cooled to room temperature, filtered.Obtained solid is dissolved in CHCl3In, use MgSO4It is dry, pass through diatomite mistake Filter, recrystallization, obtains compound 003 (13.70mmol, yield 62%), theoretical value 744.23, measured value 744.26.
[synthesis example 4]
The synthesis of compound 024
By intermediate 1-1 (118.3mmol), (3- (naphthols [2,1-b] benzene -10- acyl groups) boric acid (118.3mmol), carbonic acid Potassium (354.9mmol), tetra-triphenylphosphine palladium (2mol%) are put into round-bottomed flask, and by tetrahydrofuran (THF) (500mL) and H2O (250mL) pour into wherein, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4Drying is simultaneously Vacuum distillation, crude product is recrystallized, and obtains intermediate 2-24 (107.65mmol, yield 91%), theoretical value 711.21, is surveyed Value is 711.26.
By intermediate 2-24 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol), Double (dibenzalacetone) palladiums (3mol%), tricyclohexyl phosphine (6mol%), is placed in dioxanes (500mL) and flows back 12 small When, after the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, gained liquid pressure-reducing is distilled, dark-brown is obtained and consolidates Body, is recrystallized to give intermediate 3-24 (96.19mmol, yield 82%), theoretical value 803.34, and measured value is 803.39。
By intermediate 3-24 (22.1mmol), 2,6 dimethyl -3- bromopyridines (22.1mmol), tetra-triphenylphosphine palladium (0.76g, 3mol%) and potassium carbonate (6.11g, 44.2mmol) are dissolved in tetrahydrofuran THF (110mL) and H2In O (55mL), return Flow 12 it is small when.After the completion of reaction, reaction mixture is cooled to room temperature, is filtered.Obtained solid is dissolved in CHCl3In, use MgSO4 It is dry, filtered, recrystallized by diatomite, obtain compound 024 (13.70mmol, yield 62%), theoretical value 782.30, Measured value is 782.36.
[synthesis example 5-14]
According to intermediate in the synthetic method of above-claimed cpd 001, compound 002, compound 003 and compound 024 Synthesis, by general formulaIt is substituted for Corresponding intermediate is obtained according to identical amount ratio；
According to the synthetic method of above-claimed cpd 001, compound 002, compound 003 and compound 024, by reaction equation 2- bromopyridines in Ar1Group be substituted for 2- methyl -6- pyridine radicals, 2,6- dimethyl -5- pyridine radicals, 2- methylpyrimidines base, 4,6- dimethyl -2- pyrimidine radicals, to pyridinylphenyl, 4- (3- methylisoquinoliniums base) phenyl, 2,3- dimethyl -1,4- quinoxalines Base, 2- methylisoquinoliniums base or 2- methyl bipyridyls, and corresponding intermediate reaction, obtain corresponding compound 004,007, 009th, 011,013,015,016,017,018 and 020.
Organic electroluminescence device manufactures embodiment
[experimental example] 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 on the 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 the thickness of vacuum evaporation above layer is 60nm, N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines (hereinafter referred to as NPD) forms hole transmission layer.Then, vacuum evaporation thickness is 30nm on above-mentioned hole transmission layer 4,4'- bis- (9- carbazoles) biphenyl are main body (hereinafter referred to as CBP), and 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 Double (2- methyl -8-hydroxyquinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyls) aluminium (hereinafter referred to as BAlq) of 10nm form sky Cave barrier layer.Vacuum evaporation thickness is any one in the compound 1-14 of the invention of 40nm on above-mentioned hole blocking layers It is a, to form electron transfer layer.Then, the fluorine that thickness is 0.2nm alkali halides has been deposited in above-mentioned electron transfer layer Change lithium, form electron injecting layer.Then the aluminium that thickness is 150nm has been deposited and has formd cathode, organic electroluminescence is completed with this The preparation of luminescent device.
[comparative example]
Comparative example (1)
Except electron transfer layer material with comparative compound 1 come instead of the present invention compound in addition to, other all with it is above-mentioned The same method of experimental example is prepared for organic electroluminescence device.
<Comparative compound 1>Alq3
Comparative example (2)
Except electron transfer layer material with comparative compound 2 come instead of the present invention compound in addition to, other all with it is above-mentioned The same method of experimental example is prepared for organic electroluminescence device.
<Comparative compound 2>
Comparative example (3)
Except electron transfer layer material with comparative compound 3 come instead of the compound that represents of the present invention in addition to, other all with The same method of above-mentioned experimental example is prepared for organic electroluminescence device.
<Comparative compound 3>
To being subject to forward dc bias voltage in the organic electroluminescence device of above-mentioned preparation, Photo Research are utilized The PR-650 photometric devices measure electroluminescence characters of company, and in 5000cd/m2Benchmark gray scale under utilize The biometrics device of McScience companies manufacture determines the service life of T95.The result is shown in table 1.
[table 1]
As can be seen from the above Table 1, prepared by the use of organic luminescent compounds of the invention as electron transfer layer organic Electroluminescent device (OLED), the organic electroluminescence device phase that 1-3 is prepared as electron transfer layer compared with comparative compound Than being both in 5000cd/m2Benchmark gray scale under, have lower driving voltage and current density, higher luminous efficiency and The service life of higher.
The currently preferred specific embodiment of above description, It should be understood by those skilled in the art that the present invention is from 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 within the scope of protection of present invention.The claimed scope of the invention is by appended claims And its equivalent defines.

Claims (10)

1. a kind of organic luminescent compounds, it is characterised in that its chemical structural formula is as shown in Equation 1：
In formula：X is O or S；
Ar1For substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical；
Ar is hydrogen or benzene；
In formula dotted line indicate position can and upper phenyl.
2. organic luminescent compounds according to claim 1, it is characterised in that the organic luminescent compounds are following knots Any one in structure：
3. organic luminescent compounds according to claim 1 or 2, it is characterised in that Ar1It is taking for 6-16 for carbon number Generation or the substituted or unsubstituted aromatic heterocyclic radical that unsubstituted phenyl or carbon number are 5-11.
4. organic luminescent compounds according to claim 1 or 2, it is characterised in that Ar1It is taking for 11-16 for carbon number Generation or the substituted or unsubstituted aromatic heterocyclic radical that unsubstituted phenyl or carbon number are 6-10.
5. organic luminescent compounds according to claim 1 or 2, it is characterised in that Ar1The substitution for being 11 for carbon number Or the substituted or unsubstituted aromatic heterocyclic radical that unsubstituted phenyl or carbon number are 7.
6. organic luminescent compounds according to claim 1 or 2, it is characterised in that Ar1For pyridine radicals, picolyl, Dimethyl pyrazole piperidinyl, methylpyrimidine base, dimethyl pyrimidine base, 4- pyridinylphenyls, 4- (3- methylisoquinoliniums base) phenyl, 2,3- Dimethyl -1,4- quinoxalinyls, 2- methylisoquinoliniums base or 2- methyl bipyridyls.
7. organic luminescent compounds according to claim 1, it is characterised in that the organic luminescent compounds are following Any one of shown structure：
8. the preparation method of organic luminescent compounds according to claim 1, it is characterised in that comprise the following steps：
Chloro- [1,1'- the biphenyl] -3- formaldehyde of step 1, the 5- for substituting bromine, benzamidine hydrochloride, K3PO4It is placed in dimethyl sulfoxide (DMSO), will Mixture be heated to 90 DEG C reaction 1 it is small when, after the completion of reaction, water is added into reaction mixture, mixture is obtained by filtration light Yellow solid, chloro- 5, the 6- dicyano p-benzoquinones of 2,3- bis- are added into the solution, are stirred at room temperature 10 minutes, and reaction is completed Afterwards, filter, vacuum distillation, gained crude product is made by silica gel chromatography using the hexane solution of 0-10% ethyl acetate For eluant, eluent, intermediate 1 is obtained；
Step 2, weigh intermediate 1, compoundPotassium carbonate and tetra-triphenylphosphine palladium, and by tetrahydrochysene furan Mutter and H2O is added thereto, by mixture reflux 24 it is small when, after the completion of reaction, remove water layer, organic layer MgSO4Dry and depressurize Distillation, crude product is recrystallized, obtains intermediate
Step 3, by intermediateDouble (pinacol) two boron, potassium acetate, double (dibenzalacetone) palladiums, Tricyclohexyl phosphine, be placed in dioxanes and flow back 12 it is small when, after the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, will Gained liquid pressure-reducing distills, and obtains dark brown solid, is recrystallized to give intermediate
Step 4, by intermediateAr1- Br, tetra-triphenylphosphine palladium and potassium carbonate are dissolved in tetrahydrochysene Furans and H2In O, when reflux 12 is small, after the completion of reaction, reaction mixture is cooled to room temperature, filters the solid of precipitation, by obtained solid It is dissolved in CHCl3In, use MgSO4It is dry, filtered by diatomite, recrystallize, obtain formula 1 Shown compound；
Its synthetic route is as follows：
In formula：X is O or S；Ar1For substituted or unsubstituted phenyl or substituted or unsubstituted aromatic heterocyclic radical；Ar for hydrogen or Benzene；In formula dotted line indicate position can and upper phenyl.
9. a kind of organic electroluminescence device, it is characterised in that its electron transport layer materials is the organic light-emitting compound shown in formula 1 Thing.
10. organic luminescent compounds according to claim 1, it is characterised in that the organic luminescent compounds can answer For organic photovoltaic cell, Electronic Paper, Organophotoreceptor, organic transistor or ink-jet printing material.
CN201711261638.0A 2017-12-04 2017-12-04 A kind of organic luminescent compounds and preparation method thereof and organic electroluminescence device Pending CN108003143A (en)

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