CN109503487A - Dihydrobenzo indazole compounds, organic electroluminescence device and display device - Google Patents

Dihydrobenzo indazole compounds, organic electroluminescence device and display device Download PDF

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CN109503487A
CN109503487A CN201811552354.1A CN201811552354A CN109503487A CN 109503487 A CN109503487 A CN 109503487A CN 201811552354 A CN201811552354 A CN 201811552354A CN 109503487 A CN109503487 A CN 109503487A
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anthryl
fluorenyl
indeno
base
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CN109503487B (en
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韩锦伟
王占奇
梁新顺
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Fuyang Sineva Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

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Abstract

The present invention relates to field of display technology, more particularly to a kind of dihydrobenzo indazole compounds, organic electroluminescence device and display device.Shown in compound according to the present invention such as formula (A):Wherein, R1The naphthenic base of alkyl or substituted or unsubstituted C3~C20 selected from C1~C20；Ar1Selected from phenyl, phenanthryl, cyclopentaphenanthreneyl, two fluorenyl of spiral shell, pyrenyl, triphenylene, fluoranthene base, indeno fluorenyl, xenyl, fluorenyl, benzo fluorenyl etc.；Ar2、Ar3It is each independently selected from phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, Spirofluorene-based, pyrenyl, triphenylene, fluoranthene base, indeno fluorenyl etc..

Description

Dihydrobenzo indazole compounds, organic electroluminescence device and display device
Technical field
The present invention relates to field of display technology, send out more particularly to a kind of dihydrobenzo indazole compounds, organic electroluminescence Optical device and display device.
Background technique
Organic electroluminescence device (Organic Light Emitting Display, abbreviation OLED) is put down as novel Plate display is compared with liquid crystal display (Liquid Crystal Display, abbreviation LCD), has thin, light, wide viewing angle, master It is dynamic shine, luminescent color is continuously adjustable, at low cost, fast response time, energy consumption is small, driving voltage is low, operating temperature range is wide, gives birth to Production. art is simple, luminous efficiency is high and can Flexible Displays the advantages that, obtained the very big concern of industrial circle and scientific circles.
The development of organic electroluminescence device promotes research of the people to electroluminescent organic material.Relative to inorganic hair Luminescent material, electroluminescent organic material have the advantage that organic material processing performance is good, can pass through vapor deposition or the side of spin coating Method forms a film on any substrate；The diversity of organic molecular structure allow to by Molecular Design and the method for modification come Adjust thermal stability, mechanical performance, the luminous and electric conductivity of organic material, the space so that material is significantly improved.
What the generation of organic electroluminescent was leaned on is the carrier (electrons and holes) transmitted in organic semiconducting materials Recombination.It is well known that the electric conductivity of organic material is very poor, there is no the energy band continued in organic semiconductor, the transmission of carrier is normal It is described with jump theory.In order to make organic electroluminescence device reach breakthrough in application aspect, it is necessary to overcome organic material The difficulty of charge injection and transmittability difference.Scientists are by the adjustment of device architecture, such as increase device organic material layer Number, and so that different organic layers is played the part of different device layers, such as the functional material having can promote electronics from cathode Injection, some functional materials can promote hole to inject from anode, and some materials can promote the transmission of charge, and some materials are then It can play the role of stopping electronics or hole transport, the hair of most important various colors certainly in organic electroluminescence device Luminescent material will also achieve the purpose that match with adjacent functional material, therefore, the organic electroluminescence device of excellent in efficiency service life length Usually device architecture and various organic materials optimization collocation as a result, this is just that chemists design and develop various structures Functionalization material provides great opportunities and challenges.
Existing organic electroluminescence device generally comprises the cathode, electron injecting layer, electronics being arranged successively from top to bottom Transport layer (Electron transport Layer, abbreviation ETL), organic luminous layer (Emitting Layer, abbreviation EML), Hole transmission layer, hole injection layer, anode and substrate.The raising of organic electroluminescence device efficiency, mainly in organic light emission The formation probability of exciton is improved in layer as far as possible, therefore the organic luminous layer of organic electroluminescence device and hole adjacent thereto pass The material of defeated layer and hole injection layer plays the role of the luminous efficiency of organic electroluminescence device and brightness vital.And The material of hole transmission layer or hole injection layer in the prior art makes organic electroluminescence device driving voltage with higher With lower luminous efficiency.
Summary of the invention
The present invention provides a kind of dihydrobenzo indazole compounds, the organic electroluminescence device comprising the compound and Display device with the organic electroluminescence device, to solve the high driving electricity of organic electroluminescence device in the prior art The problem of pressure and low luminous efficiency.
According to an aspect of the present invention, a kind of dihydrobenzo indazole compounds, the compound such as formula (A) institute are provided Show:
Wherein, R1The naphthenic base of alkyl or substituted or unsubstituted C3~C20 selected from C1~C20；
Ar1Selected from phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, two fluorenyl of spiral shell, pyrenyl, triphenylene, fluoranthene base, Indeno fluorenyl, xenyl, fluorenyl, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphtho- anthryl, benzo anthryl, substituted benzene Base, substituted naphthalene, substituted anthryl, substituted phenanthryl, substituted cyclopentaphenanthreneyl, substituted two fluorenyl of spiral shell, substituted pyrene Base, substituted triphenylene, substituted fluoranthene base, substituted indeno fluorenyl, substituted xenyl, substituted fluorenyl, replace Benzo fluorenyl, substituted indeno anthryl, substituted dibenzo fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl；
Ar2、Ar3It is each independently selected from phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, Spirofluorene-based, pyrenyl, triphenylene Base, fluoranthene base, indeno fluorenyl, xenyl, terphenyl, fluorenyl, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphthanthracene Base, benzo anthryl, dihydrobenzo anthryl, tetrahydro anthryl, substituted phenyl, substituted naphthalene, substituted anthryl, substituted phenanthrene Base, substituted Spirofluorene-based, substitution pyrenyl, substituted triphenylene, substituted fluoranthene base, replaces substituted cyclopentaphenanthreneyl Indeno fluorenyl, substituted xenyl, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthryl, substituted dibenzo Fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl, substituted dihydrobenzo anthryl or substituted tetrahydro anthryl.
According to embodiment of the present invention, Ar1In, substituted phenyl, substituted anthryl, replaces substituted naphthalene Phenanthryl, substituted cyclopentaphenanthreneyl, substituted two fluorenyl of spiral shell, substituted pyrenyl, substituted triphenylene, substituted fluoranthene Base, substituted xenyl, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthryl, replaces substituted indeno fluorenyl Dibenzo fluorenyl, substituted naphtho- anthryl, in substituted benzanthracene, substituent group is each independently selected from: the alkane of C1~C20 Base, the naphthenic base of C3~C20 or phenyl.
According to embodiment of the present invention, Ar2、Ar3In, substituted phenyl, substituted anthryl, takes substituted naphthalene The phenanthryl in generation, substituted cyclopentaphenanthreneyl, substituted Spirofluorene-based, substitution pyrenyl, substituted triphenylene, substituted fluoranthene Base, substituted xenyl, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthryl, replaces substituted indeno fluorenyl Dibenzo fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl, substituted dihydrobenzo anthryl, substituted tetrahydro anthryl In, substituent group be each independently selected from: the alkyl of C1~C20, the naphthenic base of C3~C20, phenyl, naphthalene, anthryl, phenanthryl, Cyclopentaphenanthreneyl, Spirofluorene-based, pyrenyl, triphenylene, fluoranthene base, indeno fluorenyl, xenyl, fluorenyl, benzo fluorenyl, indeno anthracene Base, dibenzo fluorenyl, naphtho- anthryl or benzo anthryl.
According to embodiment of the present invention, the compound is selected from:
According to another aspect of the present invention, the preparation method of dihydrobenzo indazole compounds as described above is provided, Including dihydrobenzo indazole substituent group corresponding to what is be activated is carried out substitution reaction.
According to another aspect of the present invention, a kind of organic electroluminescence device is provided, which contains With good grounds dihydrobenzo indazole compounds of the invention.
According to embodiment of the present invention, the hole mobile material of the organic electroluminescence device includes according to this hair Bright dihydrobenzo indazole compounds.
According to embodiment of the present invention, the hole-injecting material of the organic electroluminescence device includes according to this hair Bright dihydrobenzo indazole compounds.
According to another aspect of the present invention, a kind of display device is provided, which includes according to the present invention having Organic electroluminescence devices.
Beneficial effects of the present invention are as follows:
Compound provided by the invention is used for the hole transmission layer or sky of the organic luminous layer of organic electroluminescence device Cave implanted layer improves the luminous efficiency of organic electroluminescence device, reduces the driving voltage of organic electroluminescence device.
Specific embodiment
Specific embodiment is only the description of the invention, without constituting the limitation to the content of present invention, below in conjunction with Invention is further explained and description for specific embodiment.
The present invention provides a kind of dihydrobenzo indazole compounds, the organic electroluminescence device comprising the compound and Display device with the organic electroluminescence device.
According to an aspect of the present invention, a kind of dihydrobenzo indazole compounds, the compound such as formula (A) institute are provided Show:
Wherein, R1The naphthenic base of alkyl or substituted or unsubstituted C3~C20 selected from C1~C20；
The substituent group of the naphthenic base of C3~C20 may, for example, be C1~C12 alkyl；Such as it can be methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, amyl, hexyl etc..
Ar1Selected from phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, two fluorenyl of spiral shell, pyrenyl, triphenylene, fluoranthene base, Indeno fluorenyl, xenyl, fluorenyl, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphtho- anthryl, benzo anthryl, substituted benzene Base, substituted naphthalene, substituted anthryl, substituted phenanthryl, substituted cyclopentaphenanthreneyl, substituted two fluorenyl of spiral shell, substituted pyrene Base, substituted triphenylene, substituted fluoranthene base, substituted indeno fluorenyl, substituted xenyl, substituted fluorenyl, replace Benzo fluorenyl, substituted indeno anthryl, substituted dibenzo fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl；
Ar2、Ar3It is each independently selected from phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, Spirofluorene-based, pyrenyl, triphenylene Base, fluoranthene base, indeno fluorenyl, xenyl, terphenyl, fluorenyl, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphthanthracene Base, benzo anthryl, dihydrobenzo anthryl, tetrahydro anthryl, substituted phenyl, substituted naphthalene, substituted anthryl, substituted phenanthrene Base, substituted Spirofluorene-based, substitution pyrenyl, substituted triphenylene, substituted fluoranthene base, replaces substituted cyclopentaphenanthreneyl Indeno fluorenyl, substituted xenyl, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthryl, substituted dibenzo Fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl, substituted dihydrobenzo anthryl or substituted tetrahydro anthryl.
Compound provided by the invention is used for the hole transmission layer or hole injection layer of organic electroluminescence device, is improved The luminous efficiency of organic electroluminescence device, the driving voltage for reducing organic electroluminescence device.
According to embodiment of the present invention, Ar1In, substituted phenyl, substituted anthryl, replaces substituted naphthalene Phenanthryl, substituted cyclopentaphenanthreneyl, substituted two fluorenyl of spiral shell, substituted pyrenyl, substituted triphenylene, substituted fluoranthene Base, substituted xenyl, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthryl, replaces substituted indeno fluorenyl Dibenzo fluorenyl, substituted naphtho- anthryl, in substituted benzanthracene, substituent group is each independently selected from: the alkane of C1~C20 Base, the naphthenic base of C3~C20 or phenyl.
According to embodiment of the present invention, Ar1Selected from phenyl, phenanthryl, cyclopentaphenanthreneyl, two fluorenyl of spiral shell, pyrenyl, three Phenylene, fluoranthene base, indeno fluorenyl, xenyl, fluorenyl, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphtho- anthryl, benzo The naphthalene of phenyl, phenyl substitution that anthryl, phenyl replace, substituted phenanthryl, substituted cyclopentaphenanthreneyl, takes substituted anthryl Two fluorenyl of spiral shell, substituted pyrenyl, substituted triphenylene, substituted fluoranthene base, the substituted indeno fluorenyl, substituted biphenyl in generation Base, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthryl, substituted dibenzo fluorenyl, phenyl replace naphthalene, The anthryl that phenyl replaces.According to embodiment of the present invention, Ar2、Ar3In, substituted phenyl, substituted naphthalene, replace Anthryl, substituted cyclopentaphenanthreneyl, substituted Spirofluorene-based, substitution pyrenyl, substituted triphenylene, replaces substituted phenanthryl Fluoranthene base, substituted indeno fluorenyl, substituted xenyl, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthracene Base, substituted dibenzo fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl, substituted dihydrobenzo anthryl, replace four In hydrogen anthryl, substituent group be each independently selected from: the alkyl of C1~C20, the naphthenic base of C3~C20, phenyl, naphthalene, anthryl, Phenanthryl, cyclopentaphenanthreneyl, Spirofluorene-based, pyrenyl, triphenylene, fluoranthene base, indeno fluorenyl, xenyl, fluorenyl, benzo fluorenyl, indenes And anthryl, dibenzo fluorenyl, naphtho- anthryl or benzo anthryl.
In the present invention, " substituent group is each independently selected from " refers to that substituent group can be same or different, can be independent Selection.
In the present invention, " alkyl of C1~C20 " further can be the alkyl of C1~C12, the alkyl of C1~C10, C1 The alkyl of the alkyl of~C8, C1~C6, such as can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding Base, tert-butyl, amyl, hexyl etc.." naphthenic base of C3~C20 " further can be the naphthenic base of C3~C8, C3~C6 Naphthenic base, such as can be cyclopropane, cyclobutane, pentamethylene, hexamethylene, cycloheptane, cyclooctane etc..
In the inventive solutions, substituent group can be with any position phase of any position and substituted structure Even, as long as the compound obtained according to the connection type can be prepared by certain method.
In addition, in the present invention, when some group is substituted, can be mono-substituted, two replace, be also possible to It is polysubstituted.
According to embodiment of the present invention, dihydrobenzo indazole compounds according to the present invention are selected from: A-1 to A- 75。
According to another aspect of the present invention, the preparation method of dihydrobenzo indazole compounds as described above is provided, Including dihydrobenzo indazole substituent group corresponding to what is be activated is carried out substitution reaction.
The mode of " the corresponding substituent group being activated ", activation for example can be bromination.
In order to which the compound of the present invention is explained in more detail, the synthetic method pair of above-mentioned particular compound will be enumerated below The present invention is further described.
The synthesis of compound A-1
(1) synthesis of 1- ethyl -1,2- dihydrobenzo [cd] indazole
Under nitrogen protection, 500 milliliters of DMF, 15.6 grams of (0.1mol) 1,2- dihydrobenzos are added in 1000 milliliters of there-necked flasks [cd] indazole, 5.6 grams of (0.1mol) potassium hydroxide, 1.9 grams of (0.01mol) cuprous iodides are warming up to 40 DEG C of stirrings 30 minutes, so 10.9 grams of (0.1mol) bromoethanes are added afterwards, is to slowly warm up to 60 DEG C and reacts 2 hours, then is warming up to 80 DEG C and reacts 16 hours.
Cooling adds water and ethyl acetate liquid separation, and organic layer is washed to neutrality, and magnesium sulfate is dry, silica gel column chromatography separation, stone Oily ether: ethyl acetate=10:1 (volume ratio) elution, eluent are concentrated to dryness, and obtain product 1- ethyl -1,2- dihydrobenzo 2.7 grams of [cd] indazole, yield 14.67%.
Mass Spectrometer Method has been carried out to obtained 1- ethyl -1,2- dihydrobenzo [cd] indazole, has obtained the m/e:184 of product (100%).
Nuclear-magnetism detection is carried out to obtained 1- ethyl -1,2- dihydrobenzo [cd] indazole, obtained nuclear-magnetism parsing data It is as follows:
1HNMR (500MHz, CDCl3): δ 8.35 (m, 1H), δ 7.87 (m, 1H), δ 7.64 (t, 1H), δ 7.48 (t, 1H), δ 7.28 (m, 1H), δ 6.51 (m, 1H), δ 4.57 (s, 1H), δ 3.97 (m, 2H), δ 1.55 (t, 3H).
(2) synthesis of compound shown in A-1:
Under nitrogen protection, 1000 milliliters of dry toluene, 18.4 grams of (0.1mol) 1- second are added in 2000 milliliters of there-necked flasks Base -1,2- dihydrobenzo [cd] indazole, 38.9 grams of bromo- N of (0.12mol) 4-, N- diphenylaniline, 2.9 grams of (0.005mol) Pd (dba)2(double (bis- Ya Benzyl benzylacetones) palladium), (mass concentration is for the toluene solution of 10.1 grams of (0.005mol) tri-tert-butylphosphines 10%), 24.96 grams of (0.26mol) sodium tert-butoxides, are slowly heated to flow back, and react 4 hours, are slowly dropped to room temperature, add ammonium chloride Aqueous solution washing, liquid separation.Organic layer is washed to neutrality, after magnesium sulfate is dry, silica gel column chromatography separation, and petroleum ether: ethyl acetate: Methylene chloride=5:2:1 (volume ratio) elution, eluent are concentrated to dryness, and obtain 29.9 grams of product, yield shown in formula A-1 70.02%.
Mass Spectrometer Method has been carried out to product shown in obtained formula A-1, has obtained the m/e:427 (100%) of product.
Nuclear-magnetism detection is carried out to product shown in obtained formula A-1, obtained nuclear-magnetism parsing data are as follows:
1HNMR (500MHz, CDCl3): δ 8.33 (m, 2H), δ 7.92 (m, 2H), δ 7.63 (t, 2H), δ 7.53 (m, 2H), δ 7.30~7.19 (m, 6H), δ 7.09 (m, 4H), δ 7.01 (m, 2H), δ 3.98 (m, 2H), δ 1.30 (t, 3H).
The synthesis of compound A-3
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoObtain corresponding compound A-3.
Compound A-3 is obtained, Mass Spectrometer Method, product m/e:483 are carried out.
The synthesis of compound A-12
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoObtain corresponding compound A-12.
Compound A-12 is obtained, Mass Spectrometer Method, product m/e:619 are carried out.
The synthesis of compound A-22
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoObtain corresponding compound A-22.
Compound A-22 is obtained, Mass Spectrometer Method, product m/e:527 are carried out.
The synthesis of compound A-29
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoObtain corresponding compound A-29.
Compound A-29 is obtained, Mass Spectrometer Method, product m/e:659 are carried out.
The synthesis of compound A-56
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoObtain corresponding compound A-56.
Compound A-56 is obtained, Mass Spectrometer Method, product m/e:743 are carried out.
The synthesis of compound A-61
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoTo corresponding compound A-61.
Compound A-61 is obtained, Mass Spectrometer Method, product m/e:503 are carried out.
The synthesis of compound A-62
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoObtain corresponding compound A-62.
Compound A-62 is obtained, Mass Spectrometer Method, product m/e:543 are carried out.
The synthesis of compound A-70
The synthesis of synthetic method reference compound A-1, only by the bromo- N of 4- therein, N- diphenylaniline is changed intoObtain corresponding compound A-70.
Compound A-70 is obtained, Mass Spectrometer Method, product m/e:603 are carried out.
The synthesis of compound A-73
The synthesis of synthetic method reference compound A-1, only changes bromoethane therein into bromobutane, by 4- therein Bromo- N, N- diphenylaniline change intoObtain corresponding compound A-73.
Compound A-73 is obtained, Mass Spectrometer Method, product m/e:769 are carried out.
The synthesis of compound A-74
The synthesis of synthetic method reference compound A-73, only changes bromobutane therein into bromocyclohexane, obtains phase The compound A-74 answered.
Compound A-74 is obtained, Mass Spectrometer Method, product m/e:795 are carried out.
For other compounds, also obtained using similar synthetic method.
According to another aspect of the present invention, a kind of organic electroluminescence device is provided, which contains With good grounds dihydrobenzo indazole compounds of the invention.
According to embodiment of the present invention, the hole mobile material of the organic electroluminescence device includes according to this hair Bright dihydrobenzo indazole compounds.
According to embodiment of the present invention, the hole-injecting material of the organic electroluminescence device includes according to this hair Bright dihydrobenzo indazole compounds.
The typical structure of organic electroluminescence device are as follows: substrate/anode/hole injection layer/hole transmission layer (HTL)/has Machine luminescent layer (EL)/electron transfer layer (ETL)/electron injecting layer/cathode.Organic electroluminescence device structure can be single-shot light Layer is also possible to multi-luminescent layer.
Wherein, the substrate in conventional organic electroluminescence device can be used in substrate, such as: glass or plastics.Anode can be with Using transparent high conductivity material, such as: indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), zinc oxide (ZnO).
The hole-injecting material (Hole Injection Material, abbreviation HIM) of hole injection layer, it is desirable that there is height Thermal stability (high Tg), have a lesser potential barrier with anode, can vacuum evaporation form pin-hole free films.Commonly HTM is Aromatic multi-amine class compound, mainly derivative of tri-arylamine group.
The hole mobile material (Hole Transport Material, abbreviation HTM) of hole transmission layer, it is desirable that there is height Thermal stability (high Tg), higher cavity transmission ability, can vacuum evaporation formed pin-hole free films.Commonly HTM is Aromatic multi-amine class compound, mainly derivative of tri-arylamine group.
Organic luminous layer includes material of main part (host) and guest materials, and wherein guest materials is luminescent material, such as is contaminated Material, material of main part need to have following characteristics: reversible electrochemical redox current potential, with adjacent hole transmission layer and electronics The HOMO energy level and lumo energy that transport layer matches, the good and hole to match and electron transport ability are good high Thermal stability and film forming, and suitable singlet or triplet state energy gap are used to control exciton in luminescent layer, there are also with phase Good energy transfer between the fluorescent dye or phosphorescent coloring answered.The luminescent material of organic luminous layer is needed by taking dyestuff as an example Have following characteristics: there is high fluorescence or phosphorescence quantum efficiency；The absorption spectrum of dyestuff and the emission spectrum of main body have Overlapping, i.e. main body is adapted to dyestuff energy, can effectively energy transmission from main body to dyestuff；The emission peak of red, green, blue to the greatest extent may be used Can be narrow, with the excitation purity obtained；Stability is good, is able to carry out vapor deposition etc..
The electron transport material (Electron transport Material, abbreviation ETM) of electron transfer layer requires ETM There are reversible and sufficiently high electrochemical reduction current potential, suitable HOMO energy level and LUMO (Lowest Unoccupied Molecular Orbital, lowest unoccupied molecular orbital) energy level value enables electronics preferably to inject, and is preferably provided with Hole blocking ability；Higher electron transport ability, the film forming and thermal stability having had.ETM is typically electron deficient knot The aromatic compound of the conjugate planes of structure.Electron transfer layer uses Alq3 (8-hydroxyquinoline aluminium) or TAZ (3- phenyl -4- (1 '-naphthalene) -5- benzene -1,2,4- triazole) either TPBi (1,3,5- tri- (N- phenyl -2- benzimidazole) benzene) or be derived from this three Any two kinds of collocation of kind material.
According to another aspect of the present invention, a kind of display device is provided, which includes according to the present invention having Organic electroluminescence devices.
It can be seen that the optional factor of compound according to the present invention, organic electroluminescence device and display device is more, Claim according to the present invention can be combined into different embodiments.The embodiment of the present invention is only used as to of the invention specific Description, is not intended as limitation of the present invention.Make below in conjunction with the organic electroluminescence device containing the compound of the present invention For embodiment, the present invention is described further.
The specific structure of material therefor is seen below in embodiment:
Embodiment 1
The compound of the present invention is in organic electroluminescence device as the application of hole transmission layer:
Organic electroluminescence device structure are as follows:
ITO/HIL02(100nm)/HTL(40nm)/EM1(30nm)/ETL(20nm)/LiF(0.5nm)/Al(150nm)。
One of them is comparison organic electroluminescence device, and hole mobile material selects NPB, other organic electroluminescences The hole mobile material of part selects material of the invention.
Glass substrate is selected in organic electroluminescence device production in the present embodiment, ITO makees anode material, and HIL02 makees Hole injection layer, EM1 make the material of main part of organic luminous layer, and TAZ makees electron injection as electron transport layer materials, LiF/Al Layer/cathode material.
Organic electroluminescence device preparation process in the present embodiment is as follows:
The glass substrate for being coated with transparent conductive layer (as anode) is ultrasonically treated in cleaning agent, then It rinses in deionized water, then the ultrasonic oil removing in acetone and alcohol mixed solvent, then is baked under clean environment and removes completely Water is improved and is passed with hole to improve the property on surface with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface The binding ability of defeated layer.
Above-mentioned glass substrate is placed in vacuum chamber, is evacuated to 1 × 10-5-9×10-3Pa, the vacuum evaporation on anode HIL02 is 100nm as hole injection layer, evaporation rate 0.1nm/s, vapor deposition film thickness.
The vacuum evaporation hole transmission layer on hole injection layer, evaporation rate 0.1nm/s, vapor deposition film thickness is 50nm.
Organic luminous layer of the vacuum evaporation EM1 as device on hole transmission layer, evaporation rate 0.1nm/s steam Plating total film thickness is 30nm.
Electron transfer layer of the vacuum evaporation TAZ as organic electroluminescence device on organic luminous layer；Speed is deposited in it Rate is 0.1nm/s, and vapor deposition total film thickness is 50nm.
The LiF of vacuum evaporation 0.5nm is as electron injecting layer on electron transfer layer (ETL)；
The aluminium (Al) of vacuum evaporation 150nm is used as cathode on electron injecting layer.
Organic electroluminescence device performance is shown in Table 1:
Table 1
It can see by upper table, organic electroluminescence can be improved using the compound of the present invention as hole transmission layer The luminous efficiency of part reduces the driving voltage of organic electroluminescence device.
Embodiment 2
The compound of the present invention is in organic electroluminescence device as the application of hole injection layer:
Organic electroluminescence device structure are as follows:
ITO/HIL02(100nm)/HTL(40nm)/EM1(30nm)/ETL(20nm)/LiF(0.5nm)/Al(150nm)。
One of them is comparison organic electroluminescence device, and hole-injecting material selects HIL02, other organic electroluminescents The hole-injecting material of device selects material of the invention.
Glass substrate is selected in organic electroluminescence device production in the present embodiment, ITO makees anode material, and NPB makees empty Cave transport layer, EM1 make the material of main part of organic luminous layer, TAZ as electron transport layer materials, LiF/Al make electron injecting layer/ Cathode material.
Organic electroluminescence device preparation process in the present embodiment is as follows:
The glass substrate for being coated with transparent conductive layer (as anode) is ultrasonically treated in cleaning agent, then It rinses in deionized water, then the ultrasonic oil removing in acetone and alcohol mixed solvent, then is baked under clean environment and removes completely Water is improved and is passed with hole to improve the property on surface with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface The binding ability of defeated layer.
Above-mentioned glass substrate is placed in vacuum chamber, is evacuated to 1 × 10-5-9×10-3Pa, the vacuum evaporation on anode Hole injection layer, evaporation rate 0.1nm/s, vapor deposition film thickness are 100nm.
Vacuum evaporation NPB is as hole transmission layer on hole injection layer, and evaporation rate 0.1nm/s, film thickness, which is deposited, is 50nm。
Organic luminous layer of the vacuum evaporation EM1 as device on hole transmission layer, evaporation rate 0.1nm/s steam Plating total film thickness is 30nm.
Electron transfer layer of the vacuum evaporation TAZ as organic electroluminescence device on organic luminous layer；Speed is deposited in it Rate is 0.1nm/s, and vapor deposition total film thickness is 50nm.
The LiF of vacuum evaporation 0.5nm is as electron injecting layer on electron transfer layer (ETL)；
The aluminium (Al) of vacuum evaporation 150nm is used as cathode on electron injecting layer.
Organic electroluminescence device performance see the table below:
Table 2
It can see by upper table, organic electroluminescence can be improved using the compound of the present invention as hole injection layer The luminous efficiency of part reduces the driving voltage of organic electroluminescence device.
The above, above embodiments are only described in detail to the technical solution to the application, but the above implementation The method that the explanation of example is merely used to help understand the embodiment of the present invention, should not be construed as the limitation to the embodiment of the present invention.This Any changes or substitutions that can be easily thought of by those skilled in the art, should all cover the embodiment of the present invention protection scope it It is interior.

Claims (9)

1. a kind of dihydrobenzo indazole compounds, which is characterized in that shown in the compound such as formula (A):
Wherein, R1The naphthenic base of alkyl or substituted or unsubstituted C3~C20 selected from C1~C20；
Ar1Selected from phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, two fluorenyl of spiral shell, pyrenyl, triphenylene, fluoranthene base, indenofluorene Base, fluorenyl, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphtho- anthryl, benzo anthryl, substituted phenyl, replaces xenyl Naphthalene, substituted anthryl, substituted phenanthryl, substituted cyclopentaphenanthreneyl, substituted two fluorenyl of spiral shell, substituted pyrenyl, replace Triphenylene, substituted fluoranthene base, substituted indeno fluorenyl, substituted xenyl, substituted fluorenyl, substituted benzfluorene Base, substituted indeno anthryl, substituted dibenzo fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl；
Ar2、Ar3Be each independently selected from phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, Spirofluorene-based, pyrenyl, triphenylene, Fluoranthene base, indeno fluorenyl, xenyl, terphenyl, fluorenyl, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphtho- anthryl, benzene And anthryl, dihydrobenzo anthryl, tetrahydro anthryl, substituted phenyl, substituted anthryl, substituted phenanthryl, replace substituted naphthalene Cyclopentaphenanthreneyl, the substituted Spirofluorene-based, pyrenyl that replaces, substituted triphenylene, substituted fluoranthene base, substituted indenofluorene Base, substituted fluorenyl, substituted benzo fluorenyl, substituted indeno anthryl, substituted dibenzo fluorenyl, takes substituted xenyl The naphtho- anthryl in generation, substituted benzo anthryl, substituted dihydrobenzo anthryl or substituted tetrahydro anthryl.
2. dihydrobenzo indazole compounds according to claim 1, which is characterized in that Ar1In, substituted phenyl replaces Naphthalene, substituted anthryl, substituted phenanthryl, substituted cyclopentaphenanthreneyl, substituted two fluorenyl of spiral shell, substituted pyrenyl, replace Triphenylene, substituted fluoranthene base, substituted indeno fluorenyl, substituted xenyl, substituted fluorenyl, substituted benzfluorene Base, substituted indeno anthryl, substituted dibenzo fluorenyl, substituted naphtho- anthryl, in substituted benzanthracene, substituent group is respectively Independently selected from: the alkyl of C1~C20, the naphthenic base of C3~C20 or phenyl.
3. dihydrobenzo indazole compounds according to claim 1, which is characterized in that Ar2、Ar3In, substituted phenyl, Substituted naphthalene, substituted phenanthryl, substituted cyclopentaphenanthreneyl, the substituted Spirofluorene-based, pyrenyl that replaces, takes substituted anthryl The triphenylene in generation, substituted fluoranthene base, substituted indeno fluorenyl, substituted xenyl, substituted fluorenyl, substituted benzfluorene Base, substituted indeno anthryl, substituted dibenzo fluorenyl, substituted naphtho- anthryl, substituted benzo anthryl, substituted dihydrobenzene And in anthryl, substituted tetrahydro anthryl, substituent group be each independently selected from: the alkyl of C1~C20, C3~C20 naphthenic base, Phenyl, naphthalene, anthryl, phenanthryl, cyclopentaphenanthreneyl, Spirofluorene-based, pyrenyl, triphenylene, fluoranthene base, indeno fluorenyl, xenyl, fluorenes Base, benzo fluorenyl, indeno anthryl, dibenzo fluorenyl, naphtho- anthryl or benzo anthryl.
4. dihydrobenzo indazole compounds according to claim 1, which is characterized in that the compound is selected from:
5. the preparation method of dihydrobenzo indazole compounds according to claim 1 to 4, which is characterized in that described Method includes that dihydrobenzo indazole substituent group corresponding to what is be activated is carried out substitution reaction.
6. a kind of organic electroluminescence device, which is characterized in that it is any that the organic electroluminescence device contains claim 1-4 The dihydrobenzo indazole compounds.
7. organic electroluminescence device according to claim 6, which is characterized in that the sky of the organic electroluminescence device Hole transport materials include any dihydrobenzo indazole compounds of claim 1-4.
8. organic electroluminescence device according to claim 6, which is characterized in that the sky of the organic electroluminescence device Hole injection material includes any dihydrobenzo indazole compounds of claim 1-4.
9. a kind of display device, which is characterized in that including organic electroluminescence device such as claimed in claim 6 to 8.
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CN114716329A (en) * 2022-04-01 2022-07-08 上海钥熠电子科技有限公司 Organic compound and organic photoelectric device

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JP2013109105A (en) * 2011-11-18 2013-06-06 Adeka Corp Light diffusive resin composition and light diffusion sheet using the same
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