[go: up one dir, main page]

CN110003020A - A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two - Google Patents

A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two Download PDF

Info

Publication number
CN110003020A
CN110003020A CN201910337120.3A CN201910337120A CN110003020A CN 110003020 A CN110003020 A CN 110003020A CN 201910337120 A CN201910337120 A CN 201910337120A CN 110003020 A CN110003020 A CN 110003020A
Authority
CN
China
Prior art keywords
luminescent material
compound
independently selected
organic
spiral shell
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Withdrawn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
CN201910337120.3A
Other languages
Chinese (zh)
Inventor
程丹丹
李小赢
曹占广
黄春雪
段陆萌
班全志
杭德余
李继响
李仲庆
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.)
Beijing Yanshan Gicom Photoelectric Technology Co Ltd
Original Assignee
Beijing Yanshan Gicom Photoelectric Technology Co Ltd
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 Beijing Yanshan Gicom Photoelectric Technology Co Ltd filed Critical Beijing Yanshan Gicom Photoelectric Technology Co Ltd
Priority to CN201910337120.3A priority Critical patent/CN110003020A/en
Publication of CN110003020A publication Critical patent/CN110003020A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • 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
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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]
    • H10K50/14—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
    • H10K85/631—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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms
    • 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
    • C09K2211/1025—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
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • 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
    • 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
    • H10K85/624—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
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention relates to a kind of electroluminescent organic materials fluorene structured with spiral shell two, have the structure as shown in general formula I.Electroluminescent organic material provided by the invention, based on two fluorenes of spiral shell, so as to improve glass transition temperature, molecule thermal stability is strong, has suitable HOMO and lumo energy and higher Eg, can effectively promote photoelectric properties and OLED device service life.Fragrant amine groups are introduced simultaneously, there is better planar structure and conjugated system compared with simple two fluorenes of spiral shell, synthesize, purify it is fairly simple, it is low in cost, contain methyl on phenyl ring simultaneously, so as to increase intermolecular distance, the association between compound is prevented, the probability of molecule piled up is reduced.It is less likely to occur to crystallize when vapor deposition, OLED yield rate can be effectively improved by being applied in OLED device, can effectively improve luminous efficiency, good film-forming property.The material can also be used as luminescent material use, can effectively improve the service life of luminescent material.

Description

A kind of electroluminescent organic material fluorene structured with spiral shell two and preparation method thereof with Using
Technical field
The invention belongs to ORGANIC ELECTROLUMINESCENCE DISPLAYS technical fields, and in particular to a kind of new Organic Electro Luminescent Materials and Its application in organic electroluminescence device.
Background technique
Application of organic electroluminescent (OLED) material in the fields such as information display material, organic optoelectronic material has Great researching value and fine application prospect.With the development of multimedia information technology, to flat-panel display device performance It is required that higher and higher.Current main display technology has plasma display apparatus, field emission display and organic electroluminescent Display device (OLED).Wherein, OLED has itself luminous, low-voltage direct-current driving, all solidstate, the wide, various colors in visual angle etc. Series of advantages, compared with liquid crystal display device, OLED does not need backlight, and visual angle is wider, low in energy consumption, and response speed is liquid 1000 times of crystal display device, therefore, OLED have broader practice prospect.
For the organic hole transport material reported at present since molecular weight is generally smaller, the glass transition temperature of material is lower, During materials'use, charging and discharging, material are easy crystallization repeatedly, and the homogeneity of film is destroyed, to influence materials'use Service life.Therefore, the organic hole transport material of stability and high efficiency is developed, to reduce driving voltage, device light emitting efficiency is improved, prolongs Long device lifetime has critically important practical application value.
Summary of the invention
The purpose of the present invention is to provide can carry out low voltage drive, the long-life and the OLED element of high efficiency, And it can provide the compound of such OLED element.
In order to develop the compound with aforesaid properties and use the OLED element of such compound, as a result, it has been found that, lead to The compound indicated using general formula 1 is crossed, can reach above-mentioned purpose.That is, the invention proposes a kind of novel organic electroluminescents Material has the structure as shown in general formula I:
In the general formula I, m represents-CH on phenyl ring3Substitution number, can be selected from 1,2 or 3.Specifically, 1,2 or 3- CH3May replace Formulas I ' shown in structure 1,2 and/or No. 3 position on H hydrogen atom.
As m=1 ,-CH3May replace Formulas I ' shown in hydrogen atom on 1,2 or No. 3 of structure any one position, i.e. institute State structure shown in optional ' -1 of the Formulas I freely~I ' -3 of organic material, the structure shown in ' -2 preferably such as Formulas I.
As m=2 ,-CH3May replace Formulas I ' shown in structure 1,2 and/or No. 3 any two position on hydrogen atom, i.e., Structure shown in optional ' -4 of the Formulas I freely~I ' -6 of the organic material.
As m=3 ,-CH3May replace Formulas I ' shown in 1,2 and No. 3 of the structure hydrogen atom on totally three positions, i.e., it is described Structure shown in optional ' -7 of Formulas I freely of organic material.
Ar in the general formula I1、Ar2、Ar3、Ar4It is independently represented each other the aromatic radical containing n phenyl ring and/or heteroaromatic Group.The aromatic group can be substituted or unsubstituted mononuclear aromatics, be also possible to substituted or unsubstituted polycyclic aromatic hydrocarbon；Institute Stating polycyclic aromatic hydrocarbon can be more benzene for rouge hydrocarbon, biphenyl type polycyclic aromatic hydrocarbon or condensed-nuclei aromatics.The n represents 1,2,3,4 or 5.
The Ar1、Ar2The group respectively represented may be the same or different, Ar3、Ar4The group respectively represented can be with It is identical, it can also be different.
The present invention is to Ar1、Ar2、Ar3、Ar4The group of representative carries out preferably, to further increase the comprehensive performance of material. Wherein, Ar1、Ar2It is independently represented each other the aromatic group containing n phenyl ring and/or heteroaromatic, n 2,3 or 4；Ar3、Ar4Respectively From independently representing the aromatic group containing n phenyl ring and/or heteroaromatic, n 1,2,3 or 4.Specifically:
The preferred Ar of the present invention1、Ar2It is each independently selected from following group:
It is highly preferred that Ar1、Ar2It is each independently selected from following group:
It is further preferred that Ar1、Ar2It is each independently selected from following group:
In above-mentioned each preferred embodiment, Ar1、Ar2The group of representative may be the same or different.
The preferred Ar of the present invention3、Ar4It is each independently selected from following group:
It is highly preferred that Ar3、Ar4It is each independently selected from following group:
It is further preferred that Ar3、Ar4It is each independently selected from following group:
As a preferred solution of the present invention, Ar3It is selected from
In above-mentioned each preferred embodiment, Ar3、Ar4The group of representative may be the same or different.
In above-mentioned each substituent group,It indicates to replace position.
Electroluminescent organic material shown in the further preferred general formula I of the present invention is selected from shown in following general formula I-1~I-113 Compound:
In the general formula I-1~I-113, m is independently represented each other 1,2 or 3 ,-CH3Specific substitution mode institute for example above It states.
Above-mentioned electroluminescent organic material is based on two fluorenes of spiral shell, so as to improve glass transition temperature, molecule thermostabilization Property it is strong, there is suitable HOMO and lumo energy and higher Eg, can effectively promote photoelectric properties and OLED device longevity Life.Fragrant amine groups are introduced simultaneously, there is better planar structure and conjugated system compared with simple two fluorenes of spiral shell, synthesize, mention It is pure fairly simple, it is low in cost, while containing methyl on phenyl ring, so as to increase intermolecular distance, prevent compound it Between association, reduce the probability of molecule piled up.It is less likely to occur to crystallize when vapor deposition, being applied in OLED device can be effective OLED yield rate is improved, luminous efficiency, good film-forming property can be effectively improved.The material can also be used as luminescent material use, The service life of luminescent material can be effectively improved.
Invention also provides the preparation methods of electroluminescent organic material shown in general formula I.
The reaction mechanism mechanism of reaction of the preparation method is as follows:
Include the following steps:
Using the two bromine substituent class compound A containing two fluorenes of methylspiro as starting material, withCoupling reaction occurs, obtains Compound B, then withCoupling reaction occurs, obtains final goal compound I.
Known common approach can be used to realize in above-mentioned step those skilled in the art, such as selects suitable catalysis Agent, solvent determine suitable reaction temperature, and time etc., the present invention is not particularly limited this.
The specific preparation method includes the following steps:
Using toluene as solvent, using acid chloride and tri-tert-butylphosphine as catalyst, potassium tert-butoxide is alkali, in nitrogen protection, control Temperature 80~120 DEG C under conditions of, containing two fluorenes of methylspiro, two bromine substituent class compound A withCoupling reaction occurs, obtains Compound B, under the same terms again withCoupling reaction occurs, obtains final goal compound I.
The raw materials such as above-mentioned solvent, catalyst, alkali can be closed by public commercial source or methods known in the art At obtaining.
Invention further provides application of the organic compound shown in general formula I in organic electroluminescence device.This Invent the hole mobile material that the preferably organic compound is used as hole transmission layer in organic electroluminescence device.
It include shown in general formula I of the present invention the present invention also provides a kind of organic electroluminescence device, in organic function layer Organic compound.The preferably described organic compound of the present invention is used as the hole transport material of organic function layer hole-transporting layer Material.The thickness of the hole transmission layer can be 10~50nm, preferably 27~33nm.
As a preferred solution of the present invention, above-mentioned organic electroluminescence device successively includes transparent base from the bottom to top Hole transmission layer that piece, anode layer, organic compound shown in general formula I are constituted, electroluminescence layer, electron transfer layer, electronics note Enter layer and cathode layer.
Wherein, glass substrate or flexible substrate can be selected in the material for constituting the transparent substrate, and tradition specifically can be used Substrate in organic luminescent device, such as glass substrate or plastic base, preferably use glass substrate.
Inorganic material can be selected in the material for constituting the anode layer, and tin indium oxide (ITO), zinc oxide, oxygen specifically can be selected Change at least one of tin zinc, gold, silver or copper, preferably tin indium oxide (ITO).
The material of main part for constituting the electroluminescence layer can be selected from any one in following compound, preferably CBP (bis- carbazoles of 4,4'-N, N'--biphenyl):
Dopant can also be added by constituting in the material of the electroluminescence layer, such as (piq) 2Ir (acac) [two-(1-
Phenyl isoquinolin quinoline base) acetylacetone,2,4-pentanedione iridium (III)].
The material for constituting the electron transfer layer can be selected from any one in following compound:
The material for constituting the electron injecting layer is selected from LiF, Li2O, MgO, Al2O3One of, preferably LiF.
The material choosing for constituting the cathode can be from one of lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin, preferably Aluminium.
In order to ensure playing synergistic effect in the luminescent device between the material of each layer, the present invention is also to the photophore The thickness of each layer carries out preferably in part, so that the luminescent device plays optimal resultant effect.
Specifically, the thickness of the hole transmission layer can be 10~50nm, preferably 27~33nm；The electroluminescent hair The thickness of photosphere can be 10~100nm, preferably 27~33nm；The thickness of the electron transfer layer can be 10~30nm, Preferably 18~22nm；The thickness of the electron injecting layer can be 5-~30nm, preferably 9~11nm；The cathode layer Thickness can be 50~200nm, preferably 100~200nm.
Novel OLED material provided by the invention is based on 9,9 ' spiral shell, two fluorenes, using aminated compounds as end group, by The active position of polycyclc aromatic compound introduces the arylamine class substituent group with hole transport performance, obtains a kind of tool There is the novel OLED material of hole transmission performance.Such material has a high hole mobility, preferable thin film stability and suitable The molecular entergy level of conjunction, high luminous efficiency can be used in field of organic electroluminescence, use as hole mobile material.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
The synthetic method of part main compound in the present invention is described below.
Embodiment 1
The synthesis of (compound I-20-2)
Synthetic route is as follows:
It comprises the following specific steps that:
The synthesis of compound B-20-2
500 milliliters of there-necked flasks match magnetic agitation, sequentially add potassium tert-butoxide 18.1g (0.188mol), N- after argon gas displacement ([1,1 '-biphenyl] -4- base) -9H- fluorenes -2- amine 33.34g (purity 99%, 0.1mol) and toluene 100ml.Nitrogen is replaced again After sequentially add 1.6ml tri-tert-butylphosphine and 0.23g acid chloride.After adding, it is heated to 85 DEG C.Start be added dropwise by 48.82g is formed containing two fluorenes of methylspiro, two bromine substituent class compound (A-20-2) (purity 99%, 0.1mol) and 100ml toluene Solution, 80-120 DEG C of temperature control.50 DEG C are cooled to, the hydrolysis of 100m deionized water is added, stirs 10 minutes, filtering, filter cake DMF It boils repeatedly several times, revolving obtains 65.92g white solid, purity 99%, yield 89%.
The synthesis of compound I-20-2
500 milliliters of there-necked flasks match magnetic agitation, sequentially add potassium tert-butoxide 18.1g (0.188mol), N- after argon gas displacement (4- fluorophenyl) -4 ' methyl-[1,1 '-biphenyl] -4- amine 27.73g (purity 99%, 0.1mol).Again after nitrogen displacement successively 1.6ml tri-tert-butylphosphine and 0.23g acid chloride is added.After adding, it is heated to 85 DEG C.Start to be added dropwise by compound B- The solution of 20-2 and 100ml toluene composition, 80-120 DEG C of temperature control.50 DEG C are cooled to, the hydrolysis of 100m deionized water, stirring 10 is added Minute, filtering, filter cake is boiled several times repeatedly with DMF, and revolving obtains 85.28g product, purity 99%, yield 91%.
Product MS (m/e): 937.15；Elemental analysis (C70H49FN2): theoretical value C:89.71%, H:5.27%, F: 2.03%, N:2.99%；Measured value C:89.70%, H:5.28%, F:2.03%, N:2.99%.
Embodiment 2
The synthesis of (compound I-14-2)
Synthetic route is as follows:
It comprises the following specific steps that:
The synthesis of compound B-14-2
500 milliliters of there-necked flasks match magnetic agitation, sequentially add potassium tert-butoxide 18.1g (0.188mol), N- after argon gas displacement (naphthalene -2- base) -9H- fluorenes -2- amine 30.74g (purity 99%, 0.1mol) and toluene 100ml.It is sequentially added after nitrogen displacement again 1.6ml tri-tert-butylphosphine and 0.23g acid chloride.After adding, it is heated to 85 DEG C.Start to be added dropwise and methylspiro is being contained by 48.82g The solution of two fluorenes, two bromine substituent class compound A-14-2 (purity 99%, 0.1mol) and 100ml toluene composition, temperature control 80-120 ℃.50 DEG C are cooled to, the hydrolysis of 100m deionized water is added, stirs 10 minutes, filtering, filter cake is boiled several times repeatedly with DMF, obtained 62.89g white solid, purity 99%, yield 88%.
The synthesis of compound I-14-2
500 milliliters of there-necked flasks match magnetic agitation, sequentially add potassium tert-butoxide 18.1g (0.188mol), N- after argon gas displacement (4- fluorophenyl) -5- (p-methylphenyl) pyridine -2- amine 27.83g (purity 99%, 0.1mol) and toluene 100ml.Nitrogen is set again 1.6ml tri-tert-butylphosphine and 0.23g acid chloride are sequentially added after changing.After adding, it is heated to 85 DEG C.Start to be added dropwise by chemical combination The solution of object B-14-2 and 100ml toluene composition, 80-120 DEG C of temperature control.50 DEG C are cooled to, the hydrolysis of 100m deionized water is added, stirs It mixes 10 minutes, filters, filter cake is boiled several times repeatedly with DMF, obtains 81.18g product, purity 99%, yield 89%.
Product MS (m/e): 912.10；Elemental analysis (C67H46FN3): theoretical value C:88.23%, H:5.08%, F: 2.08%, N:4.61%；Measured value C:88.22%, H:5.09%, F:2.08%, N:4.61%.
Embodiment 3
The synthesis of (compound I-113-2)
Synthetic route is as follows:
It comprises the following specific steps that:
The synthesis of compound B-113-2
500 milliliters of there-necked flasks match magnetic agitation, sequentially add potassium tert-butoxide 18.1g (0.188mol), N- after argon gas displacement (naphthalene -2- base) dibenzothiophenes -3- amine 32.54g (purity 99%, 0.1mol) and toluene 100ml.Again after nitrogen displacement successively 1.6ml tri-tert-butylphosphine and 0.23g acid chloride is added.After adding, it is heated to 85 DEG C.Start to be added dropwise by 48.82g containing methyl The solution of two fluorenes of spiral shell, two bromine substituent class compound A-113-2 (purity 99%, 0.1mol) and 100ml toluene composition, temperature control 80- 120℃.50 DEG C are cooled to, the hydrolysis of 100m deionized water is added, stirs 10 minutes, filtering, filter cake is boiled several times repeatedly with DMF, Obtain 66.31g white solid, purity 99%, yield 90.5%.
The synthesis of compound I-113-2
500 milliliters of there-necked flasks match magnetic agitation, sequentially add potassium tert-butoxide 18.1g (0.188mol), N- after argon gas displacement (4- fluorophenyl) -3- (pyridin-4-yl) aniline 26.43g (purity 99%, 0.1mol).It is sequentially added after nitrogen displacement again 1.6ml tri-tert-butylphosphine and 0.23g acid chloride.After adding, it is heated to 85 DEG C.Start to be added dropwise by compound B-113-2 and The solution of 100ml toluene composition, 80-120 DEG C of temperature control.50 DEG C are cooled to, the hydrolysis of 100m deionized water is added, stirs 10 minutes, Filtering, filter cake are boiled several times repeatedly with DMF, obtain 82.31g product, yield 87%.
Product MS (m/e): 916.11；Elemental analysis (C65H42FN3S): theoretical value C:85.22%, H:4.62%, F: 2.07%, N:4.59%, S:3.50%；Measured value C:85.20%, H:4.64%, F:2.07%, N:4.59%, S:3.50%.
Intermediate N ([1,1 '-biphenyl] -4- base) -9H- fluorenes -2- amine etc. can be from Beijing Yan Huaji used in the process of test Join photoelectricity technology corporation, Ltd.'s purchase gained.
According to embodiment 1, the technical solution of embodiment 2 and embodiment 3, it is only necessary to which the corresponding raw material of simple replacement does not change Become any substantive operations, following compound can be synthesized:
Embodiment 4:OLED device
Present embodiments provide one group of OLED device, preparation method specifically:
(1) glass substrate for being coated with ITO conductive layer is ultrasonically treated 30 minutes in cleaning agent, is rushed in deionized water It washes, at acetone/ethanol in the mixed solvent ultrasound 30 minutes, is baked to is completely dried under a clean environment, use ultraviolet rays cleaning Machine irradiates 10 minutes, and with low energy cation beam bombarded surface；
(2) the above-mentioned ito glass substrate handled well is placed in vacuum chamber, is evacuated to
1×10-5~9 × 10-4Pa vacuum evaporation compound 2-TNATA on above-mentioned anode tunic is formed with a thickness of 60nm Hole injection layer；The compound I-20-2 that vacuum evaporation embodiment 1 provides on hole injection layer as hole transmission layer, Evaporation rate is 0.2nm/s, and vapor deposition film thickness is 30nm；
(3) electroluminescence layer, concrete operations are formed on above-mentioned hole transmission layer are as follows: luminescent layer material of main part will be used as CBP [bis- carbazoles of 4,4'-N, N'--biphenyl] is placed in the cell of vacuum phase deposition equipment, by (piq) as dopant 2Ir (acac) [two-(1- phenyl isoquinolin quinoline base) acetylacetone,2,4-pentanedione iridium (III)] is placed on another room of vacuum phase deposition equipment In, two kinds of materials are evaporated simultaneously with different rates, the concentration of (piq) 2Ir (acac) is 5%, and vapor deposition total film thickness is 30nm；
(4) continue that electron transfer layer of the one layer of compound BCP as device, vapor deposition speed is deposited on the electroluminescence layer Rate is 0.2nm/s, and vapor deposition film thickness is 20nm；The structure of the BCP are as follows:
(5) continue that electron injecting layer of the one layer of LiF as device is deposited on the electron transfer layer, evaporation rate is 0.2nm/s, vapor deposition film thickness are 10nm；
(6) continue that cathode of the one layer of Al as device, evaporation rate 0.2nm/ is deposited on the electron injecting layer S, vapor deposition film thickness are 150nm；OLED device provided by the invention is obtained, OLED-1 is denoted as.
According to upper identical step, only by the compound I-20-2 in step (2) replace with embodiment 2 offer chemical combination Object I-14-2 obtains OLED-2 provided by the invention.
According to upper identical step, only by the compound I-20-2 in step (2) replace with embodiment 3 offer chemical combination Object I-113-2 obtains OLED-3 provided by the invention.
According to upper identical step, the compound I-20-2 in step (2) is only replaced with into NPB (control compounds 1), Obtain OLED-4 provided by the invention.The structure of the NPB specifically:
The present invention detects the performance of above-mentioned obtained device OLED-1~OLED-4, and testing result is as shown in table 1.
Table 1:OLED device performance testing result
From the foregoing, it will be observed that device OLED-1, OLED-2 for being prepared into using organic material shown in Formulas I provided by the invention and The operating voltage of OLED-3 is lower, and brightness under the same conditions, current efficiency is obviously than NPB as hole mobile material Device OLED-4 is much higher, and the service life of device is obviously prolonged very much.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art 's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed Range.

Claims (10)

1. a kind of electroluminescent organic material fluorene structured with spiral shell two, which is characterized in that have the structure as shown in general formula I:
In the general formula I, m be 1~3 integer；
Ar1、Ar2、Ar3、Ar4Be independently represented each other the aromatic group containing n phenyl ring and/or heteroaromatic, n be 1~5 it is whole Number.
2. luminescent material according to claim 1, which is characterized in that Ar1、Ar2It is independently represented each other containing n phenyl ring And/or the aromatic group of heteroaromatic, n 2,3 or 4；
Ar3、Ar4It is independently represented each other the aromatic group containing n phenyl ring and/or heteroaromatic, n 1,2,3 or 4.
3. luminescent material described in any one according to claim 1~2, which is characterized in that Ar1、Ar2It is each independently selected from Following group:
Ar3、Ar4It is each independently selected from following group:
4. luminescent material according to any one of claims 1 to 3, which is characterized in that Ar1、Ar2It is each independently selected from Following group:
Ar3、Ar4It is each independently selected from following group:
5. luminescent material described in any one according to claim 1~4, which is characterized in that Ar1、Ar2It is each independently selected from Following group:
Ar3、Ar4It is each independently selected from following group:
6. luminescent material described in any one according to claim 1~5, which is characterized in that Ar3It is selected from
7. luminescent material according to claim 1, which is characterized in that be selected from chemical combination shown in following general formula I-1~I-113 Object:
8. the preparation method of electroluminescent organic material described in claim 1~7 any one, which is characterized in that the reaction mechanism mechanism of reaction It is as follows:
Include the following steps:
Using the two bromine substituent class compound A containing two fluorenes of methylspiro as starting material, withCoupling reaction occurs, obtains chemical combination Object B, then withCoupling reaction occurs, obtains final goal compound I；
Preferably, the preparation method includes the following steps:
Using toluene as solvent, using acid chloride and tri-tert-butylphosphine as catalyst, potassium tert-butoxide is alkali, in nitrogen protection, temperature control 80 Under conditions of~120 DEG C, containing two fluorenes of methylspiro, two bromine substituent class compound A withCoupling reaction occurs, obtains chemical combination Object B, under the same terms again withCoupling reaction occurs, obtains final goal compound I.
9. application of the luminescent material described in claim 1~7 any one in organic electroluminescence device；
Preferably, the luminescent material is used as the hole mobile material of hole transmission layer in organic electroluminescence device.
It include shining described in claim 1~7 any one 10. a kind of organic electroluminescence device, in organic function layer Material；
Preferably, the luminescent material is used as the hole mobile material of organic function layer hole-transporting layer；
It is highly preferred that the hole transmission layer with a thickness of 10~50nm.
CN201910337120.3A 2019-04-25 2019-04-25 A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two Withdrawn CN110003020A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910337120.3A CN110003020A (en) 2019-04-25 2019-04-25 A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910337120.3A CN110003020A (en) 2019-04-25 2019-04-25 A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two

Publications (1)

Publication Number Publication Date
CN110003020A true CN110003020A (en) 2019-07-12

Family

ID=67174095

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910337120.3A Withdrawn CN110003020A (en) 2019-04-25 2019-04-25 A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two

Country Status (1)

Country Link
CN (1) CN110003020A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020083327A1 (en) * 2018-10-25 2020-04-30 常州强力电子新材料股份有限公司 Organic compound containing spirobifluorene structure and application thereof in oled device
CN113620861A (en) * 2020-12-14 2021-11-09 阜阳欣奕华材料科技有限公司 Organic electroluminescent compound and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107922312A (en) * 2015-07-29 2018-04-17 默克专利有限公司 Material for organic electroluminescence device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107922312A (en) * 2015-07-29 2018-04-17 默克专利有限公司 Material for organic electroluminescence device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020083327A1 (en) * 2018-10-25 2020-04-30 常州强力电子新材料股份有限公司 Organic compound containing spirobifluorene structure and application thereof in oled device
CN113620861A (en) * 2020-12-14 2021-11-09 阜阳欣奕华材料科技有限公司 Organic electroluminescent compound and preparation method and application thereof
CN113620861B (en) * 2020-12-14 2023-04-07 阜阳欣奕华材料科技有限公司 Organic electroluminescent compound and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Wang et al. Solution‐Processible 2, 2′‐Dimethyl‐biphenyl Cored Carbazole Dendrimers as Universal Hosts for Efficient Blue, Green, and Red Phosphorescent OLEDs
CN109776396A (en) A kind of organic compound and the preparation method and application thereof fluorene structured with spiral shell two
CN109776395A (en) A kind of cavitation material and the preparation method and application thereof that fluorine-containing spiral shell two is fluorene structured
CN110563746B (en) Novel SO2 spiro-structure-containing compound and application thereof in OLED (organic light emitting diode) device
CN109970577A (en) It is a kind of with the compound and the preparation method and application thereof fluorene structured containing methylspiro two
CN109942440A (en) A kind of OLED material and the preparation method and application thereof fluorene structured with spiral shell two
CN109503459A (en) A kind of electroluminescent organic material and its synthetic method and its application in the devices
CN110003020A (en) A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two
CN109608383A (en) A kind of electroluminescent organic material and the preparation method and application thereof
CN109970578A (en) A kind of organic compound and the preparation method and application thereof fluorene structured with 9,9 '-spiral shells two
CN109608385A (en) A kind of organic material and its preparation and application
CN109879763A (en) A kind of organic light emission cavitation material and the preparation method and application thereof fluorene structured with spiral shell two
CN109776397A (en) A kind of organic compound and the preparation method and application thereof fluorene structured with 9,9 '-spiral shells two
CN109721526A (en) A kind of organic compound and preparation method thereof and its application in the devices
CN108409584A (en) A kind of new organic materials and its application in electroluminescent device
CN100509806C (en) Novel compound
CN110143885A (en) A kind of organic compound and its application fluorene structured with spiral shell two
CN110143884A (en) A kind of organic compound and the preparation method and application thereof fluorene structured containing spiral shell two
CN109608386A (en) A kind of organic material and its application in the devices
CN109608384A (en) A kind of organic material and preparation method thereof and its application in electroluminescent device
CN109503460A (en) A kind of organic material and the preparation method and application thereof
CN110128280A (en) A kind of organic compound and the preparation method and application thereof
CN109574911A (en) A kind of luminous organic material and preparation method thereof and its application in the devices
CN108530305A (en) A kind of new organic materials and its application in display device
CN108383735A (en) A kind of organic compound and its synthetic method and application

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: 20190712

WW01 Invention patent application withdrawn after publication