CN108794374A - A kind of biindolyl class material, organic electroluminescence device and display device - Google Patents

A kind of biindolyl class material, organic electroluminescence device and display device Download PDF

Info

Publication number
CN108794374A
CN108794374A CN201810513075.8A CN201810513075A CN108794374A CN 108794374 A CN108794374 A CN 108794374A CN 201810513075 A CN201810513075 A CN 201810513075A CN 108794374 A CN108794374 A CN 108794374A
Authority
CN
China
Prior art keywords
organic electroluminescence
electroluminescence device
carbon atom
atom number
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201810513075.8A
Other languages
Chinese (zh)
Inventor
赵东敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201810513075.8A priority Critical patent/CN108794374A/en
Publication of CN108794374A publication Critical patent/CN108794374A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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
    • 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
    • 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
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/649—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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • 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 display technology fields, more particularly to a kind of biindolyl class material, organic electroluminescence device and display device.Shown in compound according to the present invention such as formula (1)：

Description

A kind of biindolyl class material, organic electroluminescence device and display device
Technical field
The present invention relates to display technology field, more particularly to a kind of biindolyl class material, organic electroluminescence device and Display device.
Background technology
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 following advantages：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 It adjusts the thermal stability of organic material, mechanical performance, shine and electric conductivity so that material is significantly improved space.
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, the transmission of carrier normal in organic semiconductor 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 Charge injects and the difficulty of transmittability difference.Scientists are by the adjustment of device architecture, such as increase device organic material layer Number, and different organic layers is made to play 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 be injected 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.Certainly in organic electroluminescence device, most important a variety of colors Luminescent material will also achieve the purpose that match with adjacent functional material.Therefore, the organic electroluminescence of excellent in efficiency long lifespan Part is typically device architecture and various organic materials optimize arranging in pairs or groups as a result, this, which is just chemists, designs and develops various structures Functionalization material provide great opportunities and challenges.
In organic electroluminescence device preparation process, one kind being known as vapour deposition method, i.e., each functional material passes through vacuum The mode of hot evaporation is plated on substrate and forms a film, this is also the mainstream technology of current industry.But the shortcomings that this technique it is also obvious that The characteristic of one side organic material itself determines, hot evaporation is carried out under the high temperature conditions for a long time, to the thermal stability of material It is required that very high；In addition prolonged stability contorting evaporation rate, keep thereon material distribution uniformity be also one very Important requirement；And high vacuum, high temperature deposition, energy consumption are higher；It is more main, because OLED material production technology itself compares Complexity, technology content is higher, thus price is more expensive, and prior art is used by vapor deposition mode, the utilization of OLED material Rate is relatively low, generally below 10%.
In the preparation process of organic electroluminescence device, another is known as solwution method, that is, uses soluble OLED materials Material, is dissolved in solvent, is coated on substrate by modes such as printing, ink-jet, spin coatings, such to form certain functional layers Method material is evenly distributed, and saves material, simplifies OLED device production technology, reduces OLED device production cost.
Invention content
Have the present invention provides a kind of biindolyl class material, the organic electroluminescence device comprising the compound and with this The display device of organic electroluminescence devices, including the organic electroluminescence device of the compound have lower driving voltage and compared with High luminous efficiency.
According to an aspect of the present invention, a kind of biindolyl class material is provided, as shown in formula (1)：
Wherein, Ar1, Ar2, Ar3 are separately selected from the aryl being made of carbon and hydrogen, the carbon that carbon atom number is 6~40 The heteroaryl being made of carbon, hydrogen, sulphur that the heteroaryl being made of carbon, hydrogen, oxygen that atomicity is 12~40, carbon atom number are 12~40 Base；The aliphatic alkyl that Ar1, Ar2, Ar3 can be 1~20 by carbon atom number, the aliphatic alcoxyl that carbon atom number is 1~20 Base, carbon atom number are replaced by 6~40 aryl being made of carbon and hydrogen；And substitution can be monosubstituted, disubstituted, take more Generation.
Further, the aryl being made of carbon and hydrogen that wherein carbon atom number is 6~40 is selected from：Phenyl, xenyl, three Phenyl, naphthalene, anthryl, triphenylene, fluorenyl, benzo fluorenyl, dibenzo fluorenyl, pyrenyl；Carbon atom number be 12~40 by carbon, The heteroaryl that hydrogen, oxygen form is selected from dibenzofuran group, naphtho- benzofuranyl, dinaphtho furyl；Carbon atom number be 12~ 40 heteroaryl being made of carbon, hydrogen, sulphur is selected from dibenzothiophene, naphtho- benzothienyl, dinaphtho thienyl；Carbon atom Number is selected from methyl, ethyl, propyl, butyl, amyl, hexyl for 1~20 aliphatic alkyl；The fat that carbon atom number is 1~20 Race's alkoxy is selected from methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy.
The biindolyl class material of the present invention preferably is selected from lower structure：
According to another aspect of the present invention, a kind of organic electroluminescence device, the organic electroluminescence device are provided Including biindolyl class material according to the present invention.
Optionally, the dyestuff of the organic electroluminescence device is the biindolyl class material according to the present invention.
Optionally, the hole mobile material of the organic electroluminescence device is the biindolyl class material according to the present invention.
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 as to the dyestuff or hole mobile material of organic electroluminescence device, is improved The luminous efficiency of organic electroluminescence device, the driving voltage for reducing organic electroluminescence device.
Specific implementation mode
Specific implementation mode 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.
Have the present invention provides a kind of biindolyl class material, the organic electroluminescence device comprising the compound and with this The display device of organic electroluminescence devices, including the organic electroluminescence device of the compound have lower driving voltage and compared with High luminous efficiency.
In addition the present invention provides the synthetic methods of the material of biindolyl class shown in the present invention：
(1) bromo- 1,1'- dimethyl -1H, the 1'H-2,2'- biindolyls of 3,3'- bis- shown in formula M successively with butyl lithium, boric acid three Methyl esters reacts, 1,1'- dimethyl -1H, 1'H- shown in formula M-1 [2,2'- biindolyl] -3,3'- hypoboric acid；
(2) [2,2'- the biindolyls] -3,3'- hypoboric acid of 1,1'- dimethyl -1H, 1'H- shown in formula M-1 andIt is prepared by reaction Compound shown in formula M-2, whereinRefer to the aromatic hydrocarbon being made of carbon and hydrogen, carbon atom number that carbon atom number is 6~40 be 12~ The 40 miscellaneous aromatic hydrocarbon being made of carbon, hydrogen, oxygen, the miscellaneous aromatic hydrocarbon being made of carbon, hydrogen, sulphur that carbon atom number is 12~40 are by one The compound formed after chlorine and a bromine substitution, for example, working as the aromatic hydrocarbon being made of carbon and hydrogen that carbon atom number is 6~40 It is corresponding when selected from anthryl, naphthalene, xenylIt is shown below respectively：
It is corresponding when the miscellaneous aromatic hydrocarbon being made of carbon, hydrogen, oxygen that carbon atom number is 12~40 is selected from dibenzofurans It is shown below：
It is corresponding when the miscellaneous aromatic hydrocarbon being made of carbon, hydrogen, sulphur that carbon atom number is 12~40 is selected from dibenzothiophenes It is shown below：
(3) compound shown in formula M-2 andReact compound shown in formula (1).
In order to which the compound of the present invention is explained in more detail, the synthetic method of particular compound will be enumerated below to this hair It is bright to be further described.
The synthesis of 1 compound P-1 of embodiment：
The synthesis of intermediate M-1：
In 1000 milliliters of there-necked flasks, 500 milliliters of tetrahydrofurans are added in nitrogen protection, 3 shown in 41.8 grams of (0.1mol) formula M, Bis- bromo- 1,1'- dimethyl -1H, 1'H-2,2'- biindolyls of 3'-, are cooled to -78 DEG C, are slowly added dropwise 137.5 milliliters (0.22mol) The hexane solution of the n-BuLi of 1.6mol/L is finished and is kept for 30 minutes in -70~-80 DEG C, is added 47.28 grams Then (0.24mol) trimethylborate is slowly increased to room temperature, stir 2 hours, and ammonium chloride solution hydrolysis, liquid separation, organic layer is added It is concentrated to dryness, ethyl acetate and alcohol mixed solvent recrystallization obtain 1,1'- dimethyl -1H, 1'H- shown in formula M-1 [2,2'- Biindolyl] 28.6 grams of -3,3'- hypoboric acid, yield 82.18%.
Nuclear-magnetism detection is carried out to product shown in obtained formula M-1, obtained nuclear-magnetism parsing data are as follows：
1HNMR (500MHz, DMSO)：δ 7.66 (m, 2H), δ 7.29 (m, 2H), δ 7.21 (m, 2H), δ 7.08 (m, 2H), δ 3.83 (s, 6H), δ 1.85 (s, 4H).
The synthesis of intermediate M-02：
2000 milliliters of there-necked flasks, nitrogen protection, 300 milliliters of toluene of addition, 300 milliliters of ethyl alcohol, 200 milliliters of water, 17.4 grams 1,1'- dimethyl-1H, 1'H- [2,2'- biindolyl] shown in (0.05mol) formula M-1-3,3'- hypoboric acid, 29.2 grams (0.1mol) The bromo- 10- chrloroanthracenes of 9-, 1.12 grams of (0.001mol) tetra-triphenylphosphine palladiums, 21.2 grams of (0.2mol) sodium carbonate are slowly heated to flow back Reaction 12 hours, cooling, liquid separation, the drying of organic layer magnesium sulfate, silica gel column chromatography separation, ethyl acetate：Petroleum ether=1：5 (bodies Product ratio) elution, eluent is concentrated to dryness, and obtains 17.6 grams of product shown in formula M-02, yield 51.64%,
Mass Spectrometer Method has been carried out to product shown in obtained formula M-02, has obtained the m/e of product：680.
The synthesis of compound P-1：
In 500 milliliters of there-necked flasks, under nitrogen protection, 150 milliliters of dry toluene, 6.8 grams of (0.01mol) formula M- are added Compound shown in 02,4.06 grams of (0.024mol) diphenylamines, 2.88 grams of (0.03mol) sodium tert-butoxides, 0.58 gram (0.001mol) Bis- (dibenzalacetone) palladiums, 2.02 grams of (0.001mol) 10% tri-tert-butylphosphine toluene solution, be heated to back flow reaction Room temperature, liquid separation are down to after 12 hours, neutrality is washed with water in organic layer, after being dried with anhydrous magnesium sulfate, crosses silica gel post separation, second Acetoacetic ester：Petroleum ether=1：5 (volume ratios) elute, and eluent is concentrated to dryness, and obtains 6.18 grams of compound, yield shown in formula P-1 It is 65.26%.
Mass Spectrometer Method has been carried out to product shown in obtained formula P-1, has obtained the m/e of product：946.
Nuclear-magnetism detection is carried out to product shown in obtained formula P-1, obtained nuclear-magnetism parsing data are as follows：
1HNMR (500MHz, CDCl3)：δ 8.21 (m, 4H), δ 8.15 (m, 4H), δ 7.81 (m, 2H), δ 7.52 (m, 10H), δ 7.32~7.20 (m, 10H), δ 7.10~6.87 (8,14H), δ 3.85 (s, 6H).
The synthesis of 2 part of compounds of the present invention of embodiment
The synthetic method of reference compound P-1, it is as needed that 9- is bromo- only in the preparation process of second step M-02 10- chrloroanthracenes change into accordinglyIn the synthesis that third walks P-1, diphenylamines therein is changed into accordinglyTool Used in precursor reactantAnd the mass spectrum of synthesized compound is listed as follows：：
The bromo- 6- chlorine pyrenes of 1- wherein used are purchased from lark prestige Science and Technology Ltd..
According to another aspect of the present invention, a kind of organic electroluminescence device, the organic electroluminescence device are provided Hole mobile material and/or dyestuff be according to the present invention biindolyl class material.
The typical structure of organic electroluminescence device is：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 can also be multi-luminescent layer.
Wherein, substrate can use the substrate in conventional organic electroluminescence device, 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), there is smaller potential barrier, vapour deposition method to prepare organic electroluminescent with anode or hole-injecting material When device, it is desirable that material energy vacuum evaporation forms pin-hole free films.Common HIM is aromatic multi-amine class compound, mainly Derivative of tri-arylamine group.When preparing organic electroluminescence device for solwution method, it is desirable that material has suitable solubility, by solution After being coated on substrate, after solution evaporation, fine and close, uniform unformed film can be formed on substrate.Common HIM material masters There is PEDOT：PSS.
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 levels 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 for controlling exciton in luminescent layer, 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：With 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, can be deposited 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 levels 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.When vapour deposition method prepares organic electroluminescence device, electron transfer layer generally uses Alq3 (8-hydroxyquinoline aluminium) either TAZ (3- phenyl -4- (1 '-naphthalene) -5- benzene -1,2,4- triazoles) or TPBi (tri- (N- of 1,3,5- Phenyl -2- benzimidazoles) benzene) or it is derived from arbitrary two kinds of the collocation of these three materials.
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.
In the preparation process of organic electroluminescence device, all functional layers therein can be all made of vapor deposition legal system It is standby, one layer therein or multilayer can also be prepared using vapour deposition method, other functional layers are prepared using solwution method, can also be incited somebody to action All functional layers therein are all made of solwution method preparation.
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 as to the specific of the present invention 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 concrete structure of material therefor is seen below in embodiment：
Embodiment 3
Hole mobile material in using the compound of the present invention as organic electroluminescence device, Organic Electricity as a comparison Electroluminescence device, hole mobile material select NPB.
Organic electroluminescence device structure is：ITO/HIL02(100nm)/HTL(40nm)/EM1(30nm)/ETL (20nm)/LiF(0.5nm)/Al(150nm)。
Organic electroluminescence device in the present embodiment selects glass substrate, ITO to make anode material in making, 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 Low energy cation beam bombarded surface is used in combination with ultraviolet light and ozone clean in water, to improve the property on surface, improves and is passed with hole 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 are 40nm.
Organic luminous layers 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 layers 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 20nm.
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：
Organic electroluminescence it can be seen that, can be improved using the compound of the present invention as hole transmission layer by upper table The luminous efficiency of part reduces the driving voltage of organic electroluminescence device.
Embodiment 4
Dyestuff in using the compound of the present invention as organic electroluminescence device prepares green organic electroluminescence Part, organic electroluminescence device as a comparison, dyestuff select D-1.
Organic electroluminescence device structure is：ITO/HIL02(100nm)/NPB(40nm)/EM2：Dyestuff [5%] (30nm)/ETL(20nm)/LiF(0.5nm)/Al(150nm)。
Organic electroluminescence device preparation process 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 Low energy cation beam bombarded surface is used in combination with ultraviolet light and ozone clean in water, to improve the property on surface, improves and is noted with hole Enter the binding ability of 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；
Vacuum evaporation NPB is as hole transmission layer on hole injection layer, and evaporation rate 0.1nm/s, film thickness, which is deposited, is 40nm；
Vacuum evaporation light emitting host material and dyestuff on hole transmission layer, as shining for organic electroluminescence device Layer, evaporation rate 0.1nm/s, vapor deposition total film thickness are 30nm；Wherein EM1：Dyestuff [5%] " refers to the doping ratio of dyestuff, i.e., The weight part ratio of material of main part and dyestuff is 100:5；
Electron transfer layers of the vacuum evaporation Alq3 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 20nm；
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：
As can be seen that under identical brightness conditions, compound using the present invention is as organic electroluminescence made from dyestuff Luminescent device with using D-1 as organic electroluminescence device made from dyestuff compared with, with lower driving voltage and higher Current efficiency.
Embodiment 5
Dyestuff in using the compound of the present invention as organic electroluminescence device, prepares blue organic electroluminescent device Part, organic electroluminescence device as a comparison, dyestuff select D-2, D-3.
Organic electroluminescence device structure is：ITO/HIL02(100nm)/NPB(40nm)/EM1：Dyestuff [5%] (30nm)/ETL(20nm)/LiF(0.5nm)/Al(150nm)。
Organic electroluminescence device preparation process 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 Low energy cation beam bombarded surface is used in combination with ultraviolet light and ozone clean in water, to improve the property on surface, improves and is noted with hole Enter the binding ability of 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；
Vacuum evaporation NPB is as hole transmission layer on hole injection layer, and evaporation rate 0.1nm/s, film thickness, which is deposited, is 40nm；
Vacuum evaporation light emitting host material and dyestuff on hole transmission layer, as shining for organic electroluminescence device Layer, evaporation rate 0.1nm/s, vapor deposition total film thickness are 30nm；Wherein EM1：Dyestuff [5%] " refers to the doping ratio of dyestuff, i.e., The weight part ratio of material of main part and dyestuff is 100:5；
Electron transfer layers of the vacuum evaporation Alq3 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 20nm；
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：
As can be seen that under identical brightness conditions, compound using the present invention is as organic electroluminescence made from dyestuff Luminescent device with using D-1 and D-2 as organic electroluminescence device made from dyestuff compared with, have lower driving voltage with Higher current efficiency.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to include these modifications and variations.

Claims (4)

1. a kind of blue organic electroluminescent device, the organic electroluminescence device includes compound shown in formula (1)：
Wherein, Ar1, Ar2, Ar3 are separately selected from the aryl being made of carbon and hydrogen, the carbon atom that carbon atom number is 6~40 Count the heteroaryl being made of carbon, hydrogen, oxygen for 12~40, the heteroaryl being made of carbon, hydrogen, sulphur that carbon atom number is 12~40；
The aliphatic alkyl that described Ar1, Ar2, Ar3 can be 1~20 by carbon atom number, the aliphatic that carbon atom number is 1~20 Alkoxy, carbon atom number are replaced by 6~40 aryl being made of carbon and hydrogen；The substitution can be it is monosubstituted, disubstituted, It is polysubstituted.
2. organic electroluminescence device according to claim 1, wherein carbon atom number are 6~40 to be made of carbon and hydrogen Aryl is selected from：Phenyl, xenyl, terphenyl, naphthalene, anthryl, triphenylene, fluorenyl, benzo fluorenyl, dibenzo fluorenyl, pyrene Base；
Carbon atom number be 12~40 the heteroaryl being made of carbon, hydrogen, oxygen be selected from dibenzofuran group, naphtho- benzofuranyl, Dinaphtho furyl；
Carbon atom number be 12~40 the heteroaryl being made of carbon, hydrogen, sulphur be selected from dibenzothiophene, naphtho- benzothienyl, Dinaphtho thienyl；
The aliphatic alkyl that carbon atom number is 1~20 is selected from methyl, ethyl, propyl, butyl, amyl, hexyl；
The aliphatic alkoxy that carbon atom number is 1~20 is selected from methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, own oxygen Base.
3. compound is selected from shown in organic electroluminescence device according to claim 1, wherein formula (1)：
4. a kind of display device, which is characterized in that include the organic electroluminescence device as described in claims 1 to 3 is any.
CN201810513075.8A 2018-05-25 2018-05-25 A kind of biindolyl class material, organic electroluminescence device and display device Withdrawn CN108794374A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810513075.8A CN108794374A (en) 2018-05-25 2018-05-25 A kind of biindolyl class material, organic electroluminescence device and display device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810513075.8A CN108794374A (en) 2018-05-25 2018-05-25 A kind of biindolyl class material, organic electroluminescence device and display device

Publications (1)

Publication Number Publication Date
CN108794374A true CN108794374A (en) 2018-11-13

Family

ID=64091750

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810513075.8A Withdrawn CN108794374A (en) 2018-05-25 2018-05-25 A kind of biindolyl class material, organic electroluminescence device and display device

Country Status (1)

Country Link
CN (1) CN108794374A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010225950A (en) * 2009-03-25 2010-10-07 Toyo Ink Mfg Co Ltd Organic electroluminescence element using polymer
KR20140006707A (en) * 2012-07-05 2014-01-16 (주)씨에스엘쏠라 New organic electroluminescent compounds and organic electroluminescent device comprising the same
KR20150109111A (en) * 2014-03-19 2015-10-01 삼성전자주식회사 Condensed compound and organic light emitting device including the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010225950A (en) * 2009-03-25 2010-10-07 Toyo Ink Mfg Co Ltd Organic electroluminescence element using polymer
KR20140006707A (en) * 2012-07-05 2014-01-16 (주)씨에스엘쏠라 New organic electroluminescent compounds and organic electroluminescent device comprising the same
KR20150109111A (en) * 2014-03-19 2015-10-01 삼성전자주식회사 Condensed compound and organic light emitting device including the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LUIS BERING ET AL.: "Aerobic, Metal-Free, and Catalytic Dehydrogenative Coupling of Heterocycles: En Route to Hedgehog Signaling Pathway Inhibitors", 《ORGANIC LETTERS》 *
SUGURU ITO ET AL.: "Two-Step Mechanochromic Luminescence of N,N’-Bis-Boc-3,3’-di(pyren-1-yl)-2,2’-biindole", 《CHEMPLUSCHEM》 *

Similar Documents

Publication Publication Date Title
CN107936955A (en) 7H benzos [de] anthracene class electroluminescent organic material, luminescent device and display
CN107955023A (en) A kind of electroluminescent organic material, luminescent device and display
CN107936952A (en) A kind of electroluminescent organic material, luminescent device and display
CN107973795A (en) A kind of electroluminescent organic material, luminescent device and display
CN108191744A (en) Benzfluorene class electroluminescent organic material, luminescent device and display
CN109206367A (en) A kind of organic electroluminescence device and display
CN109206368A (en) A kind of dihydrobenzo indazole class electroluminescent organic material
CN108623515A (en) Contain unsaturated nitrogenous heterocyclic dihydroanthracene compound, organic electroluminescence device and display device
CN109336861A (en) Dihydrobenzo indazole class electroluminescent organic material
CN108586314A (en) Dihydroanthracene compound, organic electroluminescence device and display device
CN108863896A (en) Biindolyl class material, organic electroluminescence device and display device
CN108922987A (en) Biindolyl class material, organic electroluminescence device and display device
CN108822016A (en) A kind of synthetic method of biindolyl class material
CN109053687A (en) A kind of biindolyl class display material
CN109206414A (en) Dihydrobenzo indazole class electroluminescent organic material
CN109336862A (en) A kind of organic electroluminescence device and display
CN108586269A (en) Dihydroanthracene compound, organic electroluminescence device and display device
CN108997318A (en) Biindolyl class electroluminescent organic material
CN109206412A (en) A kind of organic electroluminescence device and display
CN108586317A (en) A kind of biindolyl class material
CN108586316A (en) Dihydroanthracene compound, organic electroluminescence device and display device
CN108794374A (en) A kind of biindolyl class material, organic electroluminescence device and display device
CN108912034A (en) A kind of biindolyl class material, organic electroluminescence device and display device
CN108892632A (en) A kind of biindolyl class material
CN108892633A (en) A kind of biindolyl class material, organic electroluminescence device and display device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20181113

WW01 Invention patent application withdrawn after publication