CN107857759A - Organic luminescent compounds and preparation method and organic luminescent device - Google Patents

Organic luminescent compounds and preparation method and organic luminescent device Download PDF

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CN107857759A
CN107857759A CN201711260703.8A CN201711260703A CN107857759A CN 107857759 A CN107857759 A CN 107857759A CN 201711260703 A CN201711260703 A CN 201711260703A CN 107857759 A CN107857759 A CN 107857759A
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organic luminescent
compound
luminescent compounds
organic
substituted
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孙毅
高伟
于哲
毕岩
赵贺
王士凯
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The present invention relates to a kind of organic luminescent compounds and preparation method and organic luminescent device, is related to organic field of light emitting materials.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 luminescent device electron transport layer materials, compared with other electron transport layer materials, the organic luminescent device prepared by the use of organic luminescent compounds provided by the invention as electron transport layer materials, its luminous efficiency significantly improves, the life-span 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

Organic luminescent compounds and preparation method and organic luminescent 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 and organic light emission Device.
Background technology
OLED due to its in terms of display and illumination potential application value and receive significant attention.Material for OLED Including luminescent material, auxiliary material and electrode material.Wherein auxiliary material mainly includes carrier transmission material, carrier injects Material and charge carrier blocking materials.Carrier transmission material is hole mobile material and electron transport material.And electric transmission material Material is responsible for electronic carrier by metallic cathode transmission and injecting luminescent layer, the property of electron transport material to transmit based on electronics There can be large effect to the efficiency of OLED.The electronics can to the efficiency of OLED with larger castering action passes Defeated material should generally have following characteristic：(1) electrochemical reduction of material is reversible, and this is due to that electronics passes in organic film The process led is a series of oxidation-reduction process；(2) HOMO of material and lumo energy are suitable, make the injection barrier of electronics most It is small, there is relatively low unlatching and operating voltage, and preferably also there is hole blocking ability；(3) electron mobility of material compared with Height, so as to ensure that it is compound that electronics can be carried out in luminescent layer, it is improved the generation speed of exciton；(4) glass of material Change transition temperature and thermolytic mechanism it is higher, and then can avoid device at work caused Joule heat to the device longevity The influence of life and efficiency；(5) non-crystalline film morphology should be presented in material, so as to avoid being declined caused by light scattering or crystal Become.
Being presently available for the electron transport material of organic electroluminescence device includes：Metal complex ALq3, Liq, TPBI, BCP etc..Wherein Alq3 is the metal-organic complex for having lighting function, because electronics locomotivity is outstanding, usually as electronics Transmission material.But oriented other layer of Alq3 is mobile and has the problems such as reducing color purity in blue-light device.It it requires A kind of Novel electronic transmission material emerges, and in the absence of above mentioned problem, has high electron affinity, and be used in organic electroluminescent During device, quick electronics mobility shows high luminous efficiency.
The content of the invention
The invention solves technical problem of the prior art, there is provided the organic luminescent compounds and system of a kind of new structure Method and organic luminescent device, the organic luminescent compounds are used as the luminous effect of organic luminescent device prepared by electron transport material Rate, stability and life-span 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；
Z1~Z5For N or O, and Z1~Z5In at least one be C；
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 5-11 substituted or unsubstituted aromatic heterocyclic radical.
In the above-mentioned technical solutions, Ar1The substituted or unsubstituted phenyl or carbon number for being 11-16 for carbon number For 6-10 substituted or unsubstituted aromatic heterocyclic radical.
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, described organic luminescent compounds are any one of following shown structures：
A kind of preparation method of organic luminescent compounds, comprises the following steps：
Step 1, compound a, compound b, potassium carbonate, tetra-triphenylphosphine palladium be put into round-bottomed flask, and by tetrahydrochysene furan Mutter and H2O is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry and depressurize Distillation, crude product is recrystallized, obtains compound c；
Step 2, by compound c, compound d, K3PO 4It is placed in dimethyl sulfoxide (DMSO), heats the mixture to 90 DEG C of reactions 1 Hour, after the completion of reaction, water is added into reactant mixture, is filtrated to get faint yellow solid, then add into the solution 2,3- bis- chloro- 5,6- dicyano p-benzoquinones, are stirred at room temperature 10 minutes, after the completion of reaction, filter, and are evaporated under reduced pressure, and gained is thick Product, using the hexane solution of 0-10% ethyl acetate as eluant, eluent, obtains compound e by silica gel chromatography；
Step 3, compound e, compound f, potassium carbonate, tetra-triphenylphosphine palladium be put into round-bottomed flask, and by tetrahydrochysene furan Mutter and H2O is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry and depressurize Distillation, crude product is recrystallized, obtains compound g；
Step 4, by compound g, double (pinacol) two boron, potassium acetate, double (dibenzalacetone) palladiums, tricyclohexyl phosphine, It is placed in dioxanes and flows back 12 hours, after the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, by gained liquid It is evaporated under reduced pressure, obtains dark brown solid, be recrystallized to give compound h；
Step 5, compound h, compound i, tetra-triphenylphosphine palladium and potassium carbonate is dissolved in tetrahydrofuran and H2In O, backflow 12 hours, after the completion of reaction, reactant mixture is cooled to room temperature, filters, gained solid is dissolved in CHCl3In, use MgSO4It is dry It is dry, filtered by diatomite, recrystallize, obtain the compound shown in formula 1；
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；Z1~Z5For N or O, and Z1~Z5In at least one be C；In formula dotted line indicate position can and upper phenyl.
A kind of organic luminescent device, its electron transport layer materials are the organic luminescent compounds shown in formula 1.
The organic luminescent compounds can apply 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 luminescent device electron transport layer materials, compared with other electron transport layer materials, with provided by the invention organic The organic luminescent device that luminophor is prepared as electron transport layer materials, its luminous efficiency significantly improves, the life-span substantially changes It is kind.
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.
Embodiment
The present invention provides a kind of organic luminescent compounds, and 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；Z1~Z5For N or O, and Z1~Z5In at least one be C；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 5-11 substituted or unsubstituted aromatic heterocyclic radical.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.
Most preferably described organic luminescent compounds are any one of following shown structures：
The present invention also provides a kind of preparation method of organic luminescent compounds, comprises the following steps：
Step 1, compound a, compound b, potassium carbonate, tetra-triphenylphosphine palladium be put into round-bottomed flask, and by tetrahydrochysene furan Mutter and H2O is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry and depressurize Distillation, crude product is recrystallized, obtains compound c；
Step 2, by compound c, compound d, K3PO 4It is placed in dimethyl sulfoxide (DMSO), heats the mixture to 90 DEG C of reactions 1 Hour, after the completion of reaction, water is added into reactant mixture, is filtrated to get faint yellow solid, then add into the solution 2,3- bis- chloro- 5,6- dicyano p-benzoquinones, are stirred at room temperature 10 minutes, after the completion of reaction, filter, and are evaporated under reduced pressure, and gained is thick Product, using the hexane solution of 0-10% ethyl acetate as eluant, eluent, obtains compound e by silica gel chromatography；
Step 3, compound e, compound f, potassium carbonate, tetra-triphenylphosphine palladium be put into round-bottomed flask, and by tetrahydrochysene furan Mutter and H2O is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry and depressurize Distillation, crude product is recrystallized, obtains compound g；
Step 4, by compound g, double (pinacol) two boron, potassium acetate, double (dibenzalacetone) palladiums, tricyclohexyl phosphine, It is placed in dioxanes and flows back 12 hours, after the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, by gained liquid It is evaporated under reduced pressure, obtains dark brown solid, be recrystallized to give compound h；
Step 5, compound h, compound i, tetra-triphenylphosphine palladium and potassium carbonate is dissolved in tetrahydrofuran and H2In O, backflow 12 hours, after the completion of reaction, reactant mixture is cooled to room temperature, filters, gained solid is dissolved in CHCl3In, use MgSO4It is dry It is dry, filtered by diatomite, recrystallize, obtain the compound shown in formula 1；
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；Z1~Z5For N or O, and Z1~Z5In at least one be C；；In formula dotted line indicate position can and upper phenyl.
The present invention also provides a kind of organic luminescent device, and its electron transport layer materials is the organic light-emitting compound shown in formula 1 Thing.
The organic luminescent compounds can apply to organic photovoltaic cell, Electronic Paper, Organophotoreceptor, organic transistor Or ink-jet printing material.
By the bromo- 5- chlorobenzaldehydes (118.3mmol) of 3-, (6- bromopyridine -2- bases) 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) is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry and subtract Pressure distillation.Crude product is recrystallized, obtains 3- (6- bromopyridine -2- bases) -5- chlorobenzaldehydes (73.35mmol, yield 62%).
By intermediateReplace with According to 3- (6- bromines Pyridine -2- bases) -5- chlorobenzaldehydes preparation method, using identical mole ratio, identical catalyst, obtain centre successively Body
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 3- (6- bromopyridine -2- bases) -5- chlorobenzaldehydes (136.7mmol), benzamidine hydrochloride (273.4mmol), K3PO 4 (273.4mmol) is placed in dimethyl sulfoxide (DMSO) (DMSO), is heated the mixture to 90 DEG C and is reacted 1 hour.After the completion of reaction, to anti- Answer and water is added in mixture, be filtrated to get faint yellow solid, 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, be evaporated under reduced pressure.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 498.02, measured value 498.06.
By intermediateReplace with According to intermediate 1-1 preparation side Method, using identical mole ratio, identical catalyst, intermediate is obtained successively
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) is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry simultaneously It is evaporated under reduced pressure.Crude product is recrystallized, intermediate 2-1 (107.65mmol, yield 91%) is obtained, theoretical value 636.17, surveys Value is 636.20.
Intermediate 2-1 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol) is double (dibenzalacetone) palladium (3mol%), tricyclohexyl phosphine (6mol%), it is placed in dioxanes (500mL) and flows back 12 hours. After the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, gained liquid pressure-reducing is distilled, obtain dark brown solid, will It is recrystallized to give intermediate 3-1 (96.19mmol, yield 82%), theoretical value 728.30, measured value 728.25.
By intermediate 3-1 (22.1mmol), 2- 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), flow back 12 hours.Reaction is completed Afterwards, reactant mixture is cooled to room temperature, filtered.Gained solid is dissolved in CHCl3In, use MgSO4Dry, pass through diatomite mistake Filter, recrystallization, obtains compound 001 (13.70mmol, yield 62%), theoretical value 679.24, measured value 679.27.
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) is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry simultaneously It is evaporated under reduced pressure, crude product is recrystallized, obtains intermediate 2-2 (107.65mmol, yield 91%), theoretical value 688.19, survey Value is 688.25.
Intermediate 2-2 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol) is double (dibenzalacetone) palladium (3mol%), tricyclohexyl phosphine (6mol%), it is placed in dioxanes (500mL) and flows back 12 hours. After the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, gained liquid pressure-reducing is distilled, obtain dark brown solid, will It is recrystallized to give intermediate 3-2 (96.19mmol, yield 82%), theoretical value 779.31, measured value 779.36.
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), flow back 12 hours.Reaction is completed Afterwards, reactant mixture is cooled to room temperature, filtered.Gained solid is dissolved in CHCl3In, use MgSO4Dry, pass through diatomite mistake Filter, recrystallization, obtains compound 002 (13.70mmol, yield 62%), theoretical value 730.25, measured value 730.31.
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) is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry And be evaporated under reduced pressure, crude product is recrystallized, obtains intermediate 2-3 (107.65mmol, yield 91%), theoretical value 703.16, Measured value is 703.19.
Intermediate 2-3 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol) is double (dibenzalacetone) palladium (3mol%), tricyclohexyl phosphine (6mol%), it is placed in dioxanes (500mL) and flows back 12 hours, After the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, gained liquid pressure-reducing is distilled, obtain dark brown solid, will It is recrystallized to give intermediate 3-3 (96.19mmol, yield 82%), theoretical value 780.26, measured value 780.31.
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), flow back 12 hours.Reaction is completed Afterwards, reactant mixture is cooled to room temperature, filtered.Gained solid is dissolved in CHCl3In, use MgSO4Dry, pass through diatomite mistake Filter, recrystallization, obtains compound 003 (13.70mmol, yield 62%), theoretical value 747.23, measured value 747.29.
The synthesis of [synthesis example 4] 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) is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry simultaneously It is evaporated under reduced pressure, crude product is recrystallized, obtains intermediate 2-24 (107.65mmol, yield 91%), theoretical value 715.19, survey Value is 715.20.
By intermediate 2-24 (106.6mmol), double (pinacol) two boron (117.3mmol), potassium acetate (319.8mmol), Double (dibenzalacetone) palladiums (3mol%), tricyclohexyl phosphine (6mol%), it 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, obtained dark-brown and consolidate Body, is recrystallized to give intermediate 3-24 (96.19mmol, yield 82%), theoretical value 806.32, and measured value is 806.39。
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 Stream 12 hours.After the completion of reaction, reactant mixture is cooled to room temperature, filtered.Gained solid is dissolved in CHCl3In, use MgSO4 Dry, filtered by diatomite, recrystallize, obtain compound 024 (13.70mmol, yield 62%), theoretical value 785.29, Measured value is 785.36.
[synthesis example 5-30]
According to the synthetic method of above-claimed cpd 001, compound 002 and compound 003, in formula Mesosome 1-1, intermediate 1-2 and intermediate 1-3 are substituted for By in 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 and compound 003, by the 2- bromopyridines in reaction equation In Ar1Group is substituted for picolyl, dimethyl pyrazole piperidinyl, methylpyrimidine base, dimethyl pyrimidine base, 4- pyridine radicals benzene Base, 4- (3- methylisoquinoliniums base) phenyl, 2,3- dimethyl -1,4- quinoxalinyls, 2- methylisoquinoliniums base or 2- methyl connection pyrrole Piperidinyl, with corresponding intermediate reaction, obtain corresponding compound 004-023,025-030.
Organic luminescent device manufactures embodiment
[experimental example] green glow organic luminescent 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 10nm double (2- methyl -8-hydroxyquinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyls) aluminium (hereinafter referred to as BAlq) form sky Cave barrier layer.Vacuum evaporation thickness is any one in 40nm compound 1-14 of the invention on above-mentioned hole blocking layers It is individual, 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 negative electrode, organic light emission is completed with this The preparation of 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 luminescent 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 luminescent 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 Above-mentioned experimental example, same method are prepared for organic luminescent device.
<Comparative compound 3>
To being subject to forward dc bias voltage in the organic luminescent device of above-mentioned preparation, Photo Research companies are utilized PR-650 photometric devices measure electroluminescence characters, and in 5000cd/m2Benchmark gray scale under it is public using McScience The biometrics device of department's manufacture determines T95 life-span.It the results are 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 Luminescent device, 1-3 compares as organic luminescent device prepared by electron transfer layer compared with comparative compound, be both 5000cd/m2Benchmark gray scale under, there is lower driving voltage and current density, higher luminous efficiency and higher longevity Life.
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 change and change 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；
Z1~Z5For N or O, and Z1~Z5In at least one be C；
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 6-16 substitutions for carbon number 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 11-16 substitutions for carbon number 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 Ar1For carbon number be 11 substitutions or Unsubstituted phenyl or carbon number are 7 substituted or unsubstituted aromatic heterocyclic radical.
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 described 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：
Step 1, compound a, compound b, potassium carbonate, tetra-triphenylphosphine palladium be put into round-bottomed flask, and by tetrahydrofuran and H2O is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry and depressurize steaming Evaporate, crude product is recrystallized, obtain compound c；
Step 2, by compound c, compound d, K3PO4It is placed in dimethyl sulfoxide (DMSO), heats the mixture to 90 DEG C and react 1 hour, After the completion of reaction, water is added into reactant mixture, is filtrated to get faint yellow solid, then 2,3- bis- is added into the solution Chloro- 5,6- dicyano p-benzoquinones, it is stirred at room temperature 10 minutes, after the completion of reaction, filters, be evaporated under reduced pressure, gained crude product leads to Silica gel chromatography is crossed, using the hexane solution of 0-10% ethyl acetate as eluant, eluent, obtains compound e；
Step 3, compound e, compound f, potassium carbonate, tetra-triphenylphosphine palladium be put into round-bottomed flask, and by tetrahydrofuran and H2O is poured into wherein, and mixture is flowed back 24 hours, after the completion of reaction, removes water layer, organic layer MgSO4Dry and depressurize steaming Evaporate, crude product is recrystallized, obtain compound g；
Step 4, by compound g, double (pinacol) two boron, potassium acetate, double (dibenzalacetone) palladiums, tricyclohexyl phosphine, be placed in In dioxanes and flow back 12 hours, after the completion of reaction, mixture is cooled to room temperature, is filtered to remove salt, by gained liquid pressure-reducing Distillation, obtains dark brown solid, is recrystallized to give compound h；
Step 5, compound h, compound i, tetra-triphenylphosphine palladium and potassium carbonate is dissolved in tetrahydrofuran and H2In O, backflow 12 is small When, after the completion of reaction, reactant mixture is cooled to room temperature, filters, gained solid is dissolved in CHCl3In, use MgSO4Dry, lead to Diatomite filtering is crossed, recrystallization, obtains the compound shown in formula 1；
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 be hydrogen or Benzene；Z1~Z5For N or O, and Z1~Z5In at least one be C；In formula dotted line indicate position can and upper phenyl.
9. a kind of organic luminescent device, it is characterised in that its electron transport layer materials is the organic luminescent compounds shown in formula 1.
10. the organic luminescent compounds described in claim 1 can apply to organic photovoltaic cell, Electronic Paper, Organophotoreceptor, Organic transistor or ink-jet printing material.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019216743A1 (en) * 2018-05-11 2019-11-14 주식회사 엘지화학 Novel heterocyclic compound and organic light emitting diode using same
CN111116562A (en) * 2019-12-24 2020-05-08 吉林奥来德光电材料股份有限公司 Organic light-emitting compound and preparation method and application thereof
CN111344288A (en) * 2018-05-11 2020-06-26 株式会社Lg化学 Novel heterocyclic compound and organic light emitting device using the same
CN111848587A (en) * 2020-07-22 2020-10-30 苏州久显新材料有限公司 Partial triazine derivative, electronic device and application
KR20210065853A (en) * 2019-11-27 2021-06-04 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150129282A (en) * 2014-05-09 2015-11-19 주식회사 엠비케이 Novel compoung for organic electroluminescent device, organic electroluminescent device including the same and electric apparatus
CN105358653A (en) * 2013-07-02 2016-02-24 默克专利有限公司 Materials for electronic devices
WO2016089080A1 (en) * 2014-12-02 2016-06-09 주식회사 두산 Organic luminescent compound and organic electroluminescent device comprising same
KR20160090262A (en) * 2015-01-21 2016-07-29 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
KR20160132724A (en) * 2015-05-11 2016-11-21 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
US20170054087A1 (en) * 2015-08-17 2017-02-23 Universal Display Corporation Organic electroluminescent materials and devices

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105358653A (en) * 2013-07-02 2016-02-24 默克专利有限公司 Materials for electronic devices
KR20150129282A (en) * 2014-05-09 2015-11-19 주식회사 엠비케이 Novel compoung for organic electroluminescent device, organic electroluminescent device including the same and electric apparatus
WO2016089080A1 (en) * 2014-12-02 2016-06-09 주식회사 두산 Organic luminescent compound and organic electroluminescent device comprising same
KR20160090262A (en) * 2015-01-21 2016-07-29 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
KR20160132724A (en) * 2015-05-11 2016-11-21 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
US20170054087A1 (en) * 2015-08-17 2017-02-23 Universal Display Corporation Organic electroluminescent materials and devices

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019216743A1 (en) * 2018-05-11 2019-11-14 주식회사 엘지화학 Novel heterocyclic compound and organic light emitting diode using same
CN111344288A (en) * 2018-05-11 2020-06-26 株式会社Lg化学 Novel heterocyclic compound and organic light emitting device using the same
CN111344288B (en) * 2018-05-11 2023-05-02 株式会社Lg化学 Novel heterocyclic compound and organic light-emitting device using same
KR20210065853A (en) * 2019-11-27 2021-06-04 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same
KR102465732B1 (en) 2019-11-27 2022-11-11 주식회사 엘지화학 Novel compound and organic light emitting device comprising the same
CN111116562A (en) * 2019-12-24 2020-05-08 吉林奥来德光电材料股份有限公司 Organic light-emitting compound and preparation method and application thereof
CN111848587A (en) * 2020-07-22 2020-10-30 苏州久显新材料有限公司 Partial triazine derivative, electronic device and application

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