CN110041366A - A kind of indeno anthracene derivant compound and its application - Google Patents

A kind of indeno anthracene derivant compound and its application Download PDF

Info

Publication number
CN110041366A
CN110041366A CN201910399348.5A CN201910399348A CN110041366A CN 110041366 A CN110041366 A CN 110041366A CN 201910399348 A CN201910399348 A CN 201910399348A CN 110041366 A CN110041366 A CN 110041366A
Authority
CN
China
Prior art keywords
formula
base
group
phenyl
atom
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.)
Granted
Application number
CN201910399348.5A
Other languages
Chinese (zh)
Other versions
CN110041366B (en
Inventor
孙军
张宏科
刘凯鹏
田密
杨丹丹
何海晓
李江楠
王小伟
刘骞峰
高仁孝
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.)
Xi'an Ruilian New Material Co Ltd
Original Assignee
Xi'an Ruilian New Material 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 Xi'an Ruilian New Material Co Ltd filed Critical Xi'an Ruilian New Material Co Ltd
Priority to CN201910399348.5A priority Critical patent/CN110041366B/en
Publication of CN110041366A publication Critical patent/CN110041366A/en
Application granted granted Critical
Publication of CN110041366B publication Critical patent/CN110041366B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/64—Acridine or hydrogenated acridine ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings
    • C07F9/65335—Six-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6544—Six-membered rings
    • C07F9/6547—Six-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
    • 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
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • 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
    • 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
    • C09K2211/1018—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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • 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
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Abstract

The invention discloses a kind of indeno anthracene derivant compound and its applications, belong to electroluminescent organic material technical field；Shown in the general structure of such compound such as following formula (I): where L1、L2、L3For phenylene or substituted phenylene, n is the arbitrary integer between 0~3, Ar1、Ar2It is same or different, Ar1、Ar2Electron donating group is respectively stood alone as, X can be C atom, O atom, S atom, N atom, Si atom, and A indicates diphenyl phosphate oxygen molecule or diphenyl boron molecule derivant；Organic electroluminescence device high brightness, low-voltage, high efficiency, long service life may be implemented as the dopant material and/or material of main part of OLED in compound provided by the invention；The thermal stability with higher of material made of these compounds, is remarkably improved the stability of photoluminescence of luminescent device, is widely used in OLED luminescent device and display device.

Description

A kind of indeno anthracene derivant compound and its application
Technical field
The invention belongs to organic electroluminescent functional material and device arts, and in particular to a kind of indeno anthracene derivant Compound and its application.
Background technique
As a kind of self luminous electronic component, organic electroluminescent LED (OLED:Organic Light Emission Diodes) show that the luminescence mechanism of illumination component is under the action of DC electric field, by organic semiconductor function Electric energy is converted into the novel photoelectric information technology of luminous energy by material.Its luminous color can be individual red, green, blue, yellow light Either combination white light.The maximum feature of OLED luminescence display technology be ultra-thin, fast response time, ultralight amount, face shine and Flexible Displays, can be used for manufacturing monochromatic or full-color display as new type light source technology can also make illuminating product or novel Back light source technique is for manufacturing liquid crystal display.
According to principle of luminosity, organic electroluminescent device (organic EL element) can be divided into fluorescent type and phosphorescence type is these two types of. Voltage is applied for organic EL element, injects hole from anode and the electronics from cathode, they in luminescent layer again In conjunction with formation exciton.According to electron spin statistic law, singlet exciton and triplet exciton are generated with the ratio of 25%:75%. Fluorescent type is because used singlet exciton to shine, therefore its internal quantum can only achieve 25%.Phosphor material is by a huge sum of money Belong to element to constitute, singlet and triplet energy state can be utilized simultaneously by seeing to pass through by gap, and internal quantum efficiency can achieve 100%.Thermal activities delayed fluorescence (TADF) material is the third generation developed after organic fluorescence materials and organic phosphorescent material Luminous organic material.Such material generally has lesser singlet-triplet poor (Δ Est), and triplet excitons can be with By passed through between anti-gap be transformed into singlet exciton shine, the singlet exciton for being electrically excited lower formation and three lines can be made full use of State exciton, the internal quantum efficiency of device can achieve 100%, while material structure is controllable, and property is stablized, cheap without expensive Heavy metal, in having a extensive future for the field OLEDs.Result of study in recent years shows: TADF material acts not only as sending out Luminescent material (dopant) in photosphere, can also be sensitized dopant as the material of main part in luminescent layer, and this kind of device has The efficiency for helping improve traditional devices, improves the excitation purity of device, improves the working life of device, is a kind of with wide application The organic electroluminescent functional material of prospect.
Organic electroluminescence device is required to improve luminous efficiency, reduce driving voltage, improve durability etc..It is wherein simultaneous Gu, which is improved efficiency, becomes a big project in the industry with device lifetime.In order to prepare high performance OLED luminescent device, need to select and Using high performance OLED functional material, for the OLED functional material of corresponding different role, the basic demand needed to have is such as Under:
1, there is good thermal stability, i.e., material will not decompose during long-time is deposited, while material being required to have There is good process reproducibility；
2, the OLED luminescent device of collocation OLED functional material production is with good performance, that is, requires better effect Rate, longer service life and lower voltage.This requires material need to have suitable highest molecule occupied orbital (HOMO), The minimum non-occupied orbital of molecule (LUMO), suitable triplet energy state.
3, should have lesser singlet and triplet state can very poor △ Est (general < as TADF material material first 0.1eV), in addition there should be suitable phosphorescent lifetime.
4, in face of the increasingly urgent market demand, can the cost of material be to measure it realize the important indicator of industrialization, Therefore synthetic route is simple, and the cost of raw material is cheap to be quickly introduced market to OLED terminal material and play an important role.
In recent years, it although the development of OLED functional material achieves some breakthroughs, is applied as illumination or display, Excavation and the better material of innovation performance are needed, especially can be applied to the material of main part and TADF body of phosphorescent OLED system The organic functional material with long-life, efficient more preferable performance of system.
Summary of the invention
The object of the present invention is to provide a kind of indeno anthracene derivant compound, which is applied to as emitting layer material In organic electroluminescence device, the device performance of organic electroluminescence device can significantly improve.
The first purpose of the invention is to provide a kind of indeno anthracene derivant compound, general structure such as following formula (I) institutes Show:
In formula (I), L1、L2、L3It is phenylene or substituted phenylene；Work as L1、L2、L3When for substituted phenylene, this A little substituent groups are methyl, ethyl or cyano；N is the arbitrary integer between 0~3；
X is oxygen atom, sulphur atom, Si-m1m2、C-m1m2Or N-m3, in which: m1、m2Be respectively and independently selected from hydrogen atom, C1~ Alkyl, phenyl or the xenyl of C6；m3For aryl；
Ar1、Ar2It is electron donating group, is respectively and independently selected from substitution or unsubstituted carbazyl, formula (II), formula (III), group shown in formula (IV), formula (V), formula (VI) or formula (VII):
Work as Ar1、Ar2When being respectively and independently selected from substituted carbazyl, these substituent groups are alkyl, phenyl, the biphenyl of C1~C6 Base；
In formula (II), Ar3、Ar4It is respectively and independently selected from the substitution or unsubstituted aryl or fused ring aryl of C6~C30, C6 The substitution of~C30 or unsubstituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle replace or unsubstituted Any one in amido；
In formula (III), R1、R2It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, the alkoxy of C1~C6, cyano, trifluoro Methyl is fluorine-based；
R3、R4It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, the alkoxy of C1~C6, substitution or unsubstituted amine Base, the substitution of C6~C30 or unsubstituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, cyano, fluoroform Base is fluorine-based；
In formula (IV), T is oxygen atom, sulphur atom, C-m4m5、Si-m4m5Or N-m6；
Wherein: m4、m5It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, phenyl or xenyl；
m6For the substitution of C6~C30 or unsubstituted aryl or fused ring aryl, the substitution of C6~C30 or unsubstituted Condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, replace or unsubstituted amido in any one；
In formula (V) and formula (VI), Y is carbon atom or silicon atom；
A is group shown in formula (VIII) or formula (Ⅸ):
Wherein, R5-R10For the alkyl of C1~C6, preferably methyl, ethyl, tert-butyl.
Preferably, in the formula (II), Ar3、Ar4Be respectively and independently selected from phenyl, xenyl, terphenyl, naphthalene, amido, Carbazyl, furyl, dibenzofuran group, thienyl, dibenzothiophene, fluorenyl, dibenzopyridine base, dibenzo oxazines base Or the mute piperazine base of pheno；
Work as Ar3、Ar4Be substituted when, substituent group be methyl, isopropyl, tert-butyl, methoxyl group, phenyl, cyano, xenyl, Naphthalene, amido, carbazyl, furyl, dibenzofuran group, thienyl, dibenzothiophene, fluorenyl, dibenzopyridine base, two One of benzoxazinyl- or the mute piperazine base of pheno.
It is highly preferred that group representated by the formula (II) is selected from one of following structural formula:
Preferably, R1、R2It is respectively and independently selected from hydrogen atom, methyl, isopropyl, tert-butyl, methoxyl group, cyano, trifluoromethyl Or it is fluorine-based；
R3、R4It is respectively and independently selected from hydrogen atom, cyano, trifluoromethyl, fluorine-based, carbazyl, N- phenyl carbazole base, diphenylamines Base, dibenzofuran group, dibenzothiophene, dibenzopyridine base, dibenzo oxazines base, fluorenyl, in 9,9- dimethyl fluorenyl Any one.
It is highly preferred that group representated by the formula (III) is selected from one of following structural formula:
Preferably, in the formula (IV), m1、m2It is respectively and independently selected from hydrogen atom, methyl, ethyl, propyl, tert-butyl, benzene Base, dibenzofuran group, dibenzothiophene, dibenzopyridine base, dibenzo oxazines base, carbazyl, N- phenyl carbazole base, three Anilino-, fluorenyl, any one in 9,9- dimethyl fluorenyl；
m3Selected from hydrogen atom, phenyl, amido, xenyl, naphthalene, carbazyl, furyl, thienyl, fluorenyl, dibenzo furan It mutters base, dibenzothiophene, N- phenyl carbazole base, triphenylamine base, 9,9- dimethyl fluorenyl, dibenzofurans -4- base-(9,9- Dimethyl -9H- fluorenes -2- base)-amine, 3,9- diphenyl -9H- carbazyl, 3- dibenzofurans -4- base -9- phenyl -9H- carbazole Base, 3- (9,9- dimethyl -9H- fluorenes -1- base) -9- phenyl -9H- carbazyl, 12,12- dimethyl -12H-10- oxa--indeno [2,1-B] fluorenyl, two fluorenyl of spiral shell.
It is highly preferred that group representated by the formula (IV) is selected from one of following structural formula:
Preferably, the indeno anthracene derivant compound, one of specially following compound:
A second object of the present invention is to provide above-mentioned indeno anthracene derivant compounds in organic electroluminescence device Using.
Third object of the present invention is to provide a kind of organic electroluminescence device, including luminescent layer, the luminescent layer material Material includes indeno anthracene derivant compound described in any of the above embodiments.
Fourth object of the present invention is to provide above-mentioned organic electroluminescence device in organic electroluminescence display device and method of manufacturing same Application.
Compared with prior art, the present invention has the following advantages: a kind of indeno anthracene derivant chemical combination provided by the invention Object has suitable HOMO/LUMO value, and organic EL element high brightness, low-voltage, high efficiency and long service life may be implemented, Meanwhile the thermal stability with higher of material made of the compound of the present invention, it is remarkably improved the stable luminescence of luminescent device Property, it can be widely used in OLED luminescent device and display device and sent out as luminescent layer material of main part or thermal activities delayed fluorescence Luminescent material uses.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of the organic electroluminescent device provided in the embodiment of the present invention.
Description of symbols:
1, substrate, 2, anode layer, 3, hole injection layer, the 4, first hole transmission layer, the 5, second hole transmission layer, 6, shine Layer, 7, hole blocking layer, 8, electron transfer layer, 9, electron injecting layer, 10, cathode layer.
Specific embodiment
In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific The invention will be further described for embodiment and attached drawing, but illustrated embodiment is not as a limitation of the invention.
Experimental method and detection method described in following each embodiments are unless otherwise specified conventional method；The examination Agent and material can be commercially available on the market unless otherwise specified.
The present invention provides a kind of indeno anthracene derivant compound, shown in general structure such as following formula (I):
L1、L2、L3It is phenylene or substituted phenylene；Work as L1、L2、L3When for substituted phenylene, these substituent groups For methyl, ethyl or cyano；Arbitrary integer of the n between 0-3；
Preferably, 0,1 or 2 n；
X is oxygen atom, sulphur atom, Si-m1m2、C-m1m2Or N-m3, in which: m1、m2Be respectively and independently selected from hydrogen atom, C1~ Alkyl, phenyl or the xenyl of C6；m3For aryl；
Ar1、Ar2It is electron donating group, is respectively and independently selected from substitution or unsubstituted carbazyl, formula (II), formula (III), group shown in formula (IV), formula (V), formula (VI) or formula (VII):
Work as Ar1、Ar2When being respectively and independently selected from substituted carbazyl, these substituent groups are alkyl, phenyl, the biphenyl of C1~C6 Base；
In formula (II), Ar3、Ar4It is respectively and independently selected from the substitution or unsubstituted aryl or fused ring aryl of C6~C30, C6 The substitution of~C30 or unsubstituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle replace or unsubstituted Any one in amido；
In formula (III), R1、R2It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, the alkoxy of C1~C6, cyano, trifluoro Methyl is fluorine-based；
R3、R4It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, the alkoxy of C1~C6, substitution or unsubstituted amine Base, the substitution of C6~C30 or unsubstituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, cyano, fluoroform Base is fluorine-based；
In formula (IV), T is oxygen atom, sulphur atom, C-m4m5、Si-m4m5Or N-m6；
Wherein: m4、m5It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, phenyl or xenyl；
m6For the substitution of C6~C30 or unsubstituted aryl or fused ring aryl, the substitution of C6~C30 or unsubstituted Condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, replace or unsubstituted amido in any one；
In formula (V) and formula (VI), Y is carbon atom or silicon atom；
A is group shown in formula (VIII) or formula (Ⅸ):
Wherein, R5-R10For the alkyl of C1~C6, preferably methyl, ethyl, tert-butyl.
A kind of small molecule compound provided by the invention, indeno anthracene derivant are connect at 9,10 of anthracene by benzene bridging or directly The groups such as the mute piperazine of furans, carbazole, thiophene, fluorenes, heteroaryl amino, acridine, pheno, the mute piperazine of thiophene are connect in succession, while in anthra five-membered ring Upper bridging diphenyl phosphate oxygen ligand or boryl ligand are built into bipolarity compound, the doping as organic electroluminescent LED Material or material of main part may be implemented organic electroluminescent (EL) element and realize high brightness, low-voltage, high efficiency, service life It is long.Phosphoroso- group is linked as the parent of core using indeno anthracene derivant or boryl ligand shows stronger electron-withdrawing ability, Electron donating group is connect by benzene bridge or without benzene bridging on parent, having constructed has to-receptor bipolar materials, such material tool There are lesser singlet energy and triplet energy state poor (△ Est), can be realized triplet energy state and inverted to singlet energy, from And there is thermal activities delay photoluminescent property (TADF).Outstanding property, a side are shown when institute's invention material is as material of main part Its bipolarity feature of face is effectively enriched hole and electronics in luminescent layer, increases the recombination region of exciton, effectively raises The efficiency of device and service life reduce the decaying of efficiency；It on the other hand can be effective as the material of main part with TADF property Sensitized luminescence material, the effective efficiency for promoting device and service life and the spectrum that TADF material can be optimized, promotion TADF device The excitation purity of part.As TADF luminescent material, the material invented is available different luminous by the modification of different substituents The material of color, internal quantum efficiency significantly improve.
In the following, providing the specific synthetic method of several intermediates corresponding to preparation above compound first.
(1) synthesis of intermediate 1-2
It is passed through nitrogen in 2L there-necked flask, sequentially adds 1L methylene chloride, 53.7g alchlor is cooled to 0 DEG C, then 100g intermediate 1-1 is added, the 200ml DCM solution of 54.3g phthalic anhydride is added dropwise in stirring after being completely dissolved raw material；It is added dropwise After keep this temperature the reaction was continued 6h, TLC monitoring intermediate 1-1 to completely consume, stop reaction；Reaction solution is poured into cold In the hydrochloric acid solution of 6M, rear static liquid separation is sufficiently stirred, organic phase is washed to neutrality, and concentration gained is white after anhydrous sodium sulfate is dry Color solid is added in 400ml phosphoric acid, is heated to 130 DEG C and is stirred to react 3h；It is down to room temperature, reaction solution pours into ice water, is added Sodium hydroxide solution adjusts pH to neutrality, filters, filter cake is washed to neutrality；It is boiled after filter cake is dried with methanol and washes purifying, obtained shallowly Yellow solid 108.6g, i.e. intermediate 1-2, yield 73.6%.
The magnetic resonance spectroscopy data of intermediate 1-2:1H NMR(400MHz,CDCl3)δ8.38(s,1H),8.09(s,1H), 7.80 (d, J=7.6,2H), 7.73 (m, 2H), 7.55 (d, J=7.6,3H), 1.67 (s, 6H).
(2) synthesis of intermediate 1-3
1L isopropanol is added in 2L there-necked flask, then 93.8g sodium borohydride is added portionwise in 100g intermediate 1-2, feed After stirring at normal temperature react 1h, be then heated to reflux the reaction was continued 5h, TLC monitoring intermediate 1-2 and completely consume, stop anti- It answers；It is cooled to room temperature reaction solution and pours into stirring precipitation solid in 3 times of volume of water, filter, filter cake is washed to neutrality；Filter cake is added It is heated to back flow reaction 3h into the hydrochloric acid solution of 2M, is cooled to room temperature filtering, filter cake is washed to neutrality, with ethyl alcohol weight after drying Crystallization, obtains yellow solid 80.7g, i.e. intermediate 1-3, yield 87.2%.
The magnetic resonance spectroscopy data of intermediate 1-3:1H NMR (400MHz, CDCl3) δ 7.95 (d, J=7.2,1H), 7.78- 7.83 (m, 2H), 7.61-7.68 (m, 5H), 7.52 (s, 1H), 7.32 (d, J=7.2,2H), 1.63 (s, 6H)；
(3) synthesis of intermediate 1-4
It is passed through nitrogen in 1L there-necked flask, sequentially adds 400ml THF, 40g intermediate 1-3 is cooled to -78 DEG C, then The butyl lithium of 47ml 2.5M is slowly added dropwise, this temperature is kept to be stirred to react 1h after being added dropwise, 23.6g diphenyl is then added Saturated ammonium chloride solution quenching reaction is added after keeping this temperature the reaction was continued 3h in phosphonium chloride；It is removed under reduced pressure after being warmed to room temperature THF, filtering, filter cake is added in 50ml hydrogen peroxide after being washed to neutrality, 40 DEG C be stirred to react 3h after filter, during filter cake is washed to Property.Re crystallization from toluene is used after filter cake is dried, and obtains light yellow solid 40.4g, i.e. intermediate 1-4, yield 76.3%.
The magnetic resonance spectroscopy data of intermediate 1-4:1H NMR (400MHz, CDCl3) δ 8.09 (d, J=7.6,1H), 7.83 (s, 1H), 7.64-7.68 (m, 4H), 7.52-7.56 (m, 3H), 7.44-7.47 (td, J=7.6,4H), 7.32-7.40 (m, 8H),1.73(s,6H)。
(4) synthesis of intermediate 1-5
40g intermediate 1-4,200ml DMF are added in 500ml there-necked flask, stirring is added after being completely dissolved raw material Room temperature is down to after being warming up to 60 DEG C after 28.8g NBS, stirring at normal temperature reaction 2h the reaction was continued 4h.Reaction solution pours into 3 times of volume of water Solid, filtering is precipitated in middle stirring, and filter cake is washed to neutrality；Filter cake is added to flow back to boil in the n-hexane of 8 times of volumes and washes 3h, is dropped It is filtered after to room temperature, obtains light yellow solid 50.5g, yield 95.8%.
The magnetic resonance spectroscopy data of intermediate 1-5:1H NMR (400MHz, CDCl3) δ 8.34 (s, 1H), 8.06 (d, J= 7.6,1H), 7.67 (d, J=7.2,2H), 7.52-7.56 (m, 3H), 7.44-7.47 (td, J=7.6,4H), 7.32-7.40 (m,8H),1.73(s,6H)。
(5) synthesis of intermediate 2-1
Synthesis step with intermediate 1-4 synthesis, the difference is that: by diphenyl phosphine chloride replace with 46.8g bis- (2, 4,6- triisopropyl phenyl) boron fluoride, obtain 52.3g intermediate 2-1, yield 68.7%.
The nuclear magnetic spectrogram data of intermediate 2-1:1H NMR (400MHz, CDCl3) δ 8.12 (d, J=7.6,1H), 7.83 (s, 1H), 7.61-7.68 (m, 5H), 7.52 (s, 1H), 7.40 (d, J=7.6,1H), 7.32 (d, J=7.2,2H), 6.80 (s, 4H), 3.12 (m, 6H), 1.73 (s, 6H), 1.29 (d, J=8.4,36H).
(6) synthesis of intermediate 2-2
Synthesis step with intermediate 1-5 synthesis, the difference is that: intermediate 1-4 is replaced with into 50g intermediate 2-1, NBS dosage is 25.0g, obtains 56.6g intermediate 2-2, yield 92.6%.
The nuclear magnetic spectrogram data of intermediate 2-2:1H NMR (400MHz, CDCl3) δ 8.34 (s, 1H), 8.12 (d, J= 7.6,1H), 7.58-7.67 (m, 4H), 7.40 (d, J=7.6,1H), 7.32 (d, J=7.2,2H), 6.80 (s, 4H), 3.12 (m, 6H), 1.73 (s, 6H), 1.29 (d, J=8.4,36H).
(7) synthesis of intermediate 3-2
Synthesis step with intermediate 1-2, the difference is that: alchlor dosage be 59.4g, intermediate 1-1 is replaced For 100g intermediate 3-1, the DCM solution usage of phthalic anhydride is the 200ml DCM solution of 60.1g phthalic anhydride, is obtained 117.2g intermediate 3-2, yield 76.9%.
The nuclear magnetic spectrogram data of intermediate 3-2:1H NMR(400MHz,CDCl3)δ8.03(s,1H),7.96(s,1H), 7.80 (d, J=7.6,2H), 7.55-7.58 (m, 3H), 7.38 (d, J=7.2,1H), 7.30 (d, J=7.2,1H).
(8) synthesis of intermediate 3-3
Synthesis step with intermediate 1-3 synthesis, the difference is that: intermediate 1-2 is replaced with into 110g intermediate 3- 2, sodium borohydride dosage is 110.3g, obtains 93.2g intermediate 3-3, yield 92.1%.
The nuclear magnetic spectrogram data of intermediate 3-3:1H NMR(400MHz,CDCl3)δ7.67(m,4H),7.59(s,1H), 7.49(s,1H),7.38-7.42(m,2H),7.30-7.32(m,3H)。
(9) synthesis of intermediate 3-4
Synthesis step with intermediate 1-4, the difference is that: intermediate 1-3 is replaced with into intermediate 3-3, butyl lithium Dosage is 50ml, and the dosage of diphenyl phosphine chloride is 25.4g, obtains 43.9g intermediate 3-4, yield 81.3%.
The nuclear magnetic spectrogram data of intermediate 3-4:1H NMR(400MHz,CDCl3)δ7.68(m,4H),7.46-7.48(m, 4H), 7.38-7.41 (m, 6H), 7.32-7.35 (m, 6H), 7.12 (d, J=7.6,1H).
(10) synthesis of intermediate 3-5
Synthesis step with intermediate 1-5 synthesis, the difference is that: intermediate 1-4 is replaced with into intermediate 3-4, NBS Dosage be 30.4g, obtain 47.9g intermediate 3-5, yield 89.6%.
The magnetic resonance spectroscopy data of intermediate 3-5:1H NMR (400MHz, CDCl3) δ 7.67 (d, J=7.2,2H), 7.46- 7.48 (m, 4H), 7.38-7.41 (m, 6H), 7.32-7.35 (m, 6H), 7.12 (d, J=7.6,1H).
(11) synthesis of intermediate 4-1
Synthesis step with intermediate 2-1 synthesis, the difference is that: intermediate 1-3 is replaced with into intermediate 3-3, fourth The dosage of base lithium is 51ml, and the dosage of two (2,4,6- triisopropyl phenyl) boron fluorides is 50.3g, obtains 58.2g intermediate 4- 1, yield 73.8%.
The magnetic resonance spectroscopy data of intermediate 4-1:1H NMR(400MHz,CDCl3)δ7.67(m,4H),7.49-7.51(m, 2H), 7.40-7.42 (m, 2H), 7.32 (d, J=7.2,2H), 7.12 (d, J=7.6,1H), 6.80 (s, 4H), 3.12 (m, 6H), 1.29 (d, J=8.4,36H).
(12) synthesis of intermediate 4-2
Synthesis step with intermediate 2-2 synthesis, the difference is that: intermediate 2-1 is replaced with into intermediate 4-1, NBS Dosage be 26.0g, obtain 58.9g intermediate 4-2, yield 95.8%.
The magnetic resonance spectroscopy data of intermediate 4-2:1H NMR (400MHz, CDCl3) δ 7.67 (d, J=7.6,2H), 7.49- 7.51 (m, 2H), 7.40-7.42 (m, 2H), 7.32 (d, J=7.2,2H), 7.12 (d, J=7.6,1H), 6.80 (s, 4H), 3.12 (m, 6H), 1.29 (d, J=8.4,36H).
(13) synthesis of intermediate 5-1
It is passed through nitrogen in 1L there-necked flask, sequentially adds 400ml THF, 35.2g 9- (4- bromophenyl) carbazole, stirring makes Raw material is cooled to -78 DEG C after being completely dissolved, the butyl lithium of 44ml 2.5M is then slowly added dropwise, this temperature is kept after being added dropwise It is stirred to react 1h, 20g intermediate 1-2 is then added, this temperature is kept the reaction was continued saturated ammonium chloride solution is added after 3h and be quenched Reaction.It removes THF after being warmed to room temperature under reduced pressure, filters, filter cake is added in 180ml acetic acid after being washed to neutrality, and it is dense that 30ml is added Hydrochloric acid pours into stirring in the ice water of 3 times of volumes after stirring at normal temperature reaction 4h and solid, filtering is precipitated, and filter cake is washed to neutrality.It will filter Column is crossed with toluene after cake drying and is recrystallized, and white solid 29.6g intermediate 5-1, yield 69.7% are obtained.
The magnetic resonance spectroscopy data of intermediate 5-1:1H NMR (400MHz, CDCl3) δ 7.95 (d, J=7.6,1H), 7.83 (s, 1H), 7.78 (s, 1H), 7.68 (d, J=7.2,2H), 7.52-7.61 (m, 10H), 7.40 (d, J=7.2,4H), 7.32- 7.35 (m, 6H), 7.08 (td, J=7.2,4H), 7.00 (td, J=7.2,4H), 1.73 (s, 6H).
(14) synthesis of intermediate 6-1
Synthesis step with intermediate 5-1, the difference is that: the dosage of 9- (4- bromophenyl) carbazole be 37.6g, butyl lithium Dosage be 47ml, intermediate 1-2 is replaced with into intermediate 3-2, obtains 31.9g intermediate 6-1, yield 72.6%.
The magnetic resonance spectroscopy data of intermediate 6-1:1H NMR (400MHz, CDCl3) δ 7.68 (d, J=7.2,2H), 7.52- 7.58 (m, 10H), 7.38-7.42 (m, 6H), 7.30-7.32 (m, 7H), 7.08 (td, J=7.2,4H), 7.00 (td, J= 7.2,4H)。
We provide the synthetic method of these compounds specifically by taking the indeno anthracene derivant compound of part as an example below.
Embodiment 1
It is passed through nitrogen in 1L there-necked flask, sequentially adds 12.8g carbazole, 20g intermediate 1-5,16.9g potassium carbonate, 0.81g 6 ether of 18- crown-, 400ml DMF, stirring are added 0.58g cuprous iodide after being completely dissolved to raw material, are heated to 130 DEG C and are stirred to react 10h, TLC monitoring compound 1-5 are completely consumed, and are stopped reaction, are cooled to room temperature and pour into reaction solution in 3 times of volume of water, stir Solid, filtering is precipitated, filter cake is washed to neutrality, is dissolved after filter cake is dried with toluene, crosses heat-insulation column, and eluent concentration is tied again Crystalline substance obtains white solid 20.8g, i.e. compound 1, yield 82.3%.
The magnetic resonance spectroscopy data of compound 1:1H NMR (400MHz, CDCl3) δ 8.08 (d, J=7.6,1H), 7.67- 7.71 (m, 4H), 7.52-7.55 (m, 6H), 7.46 (td, J=7.6,4H), 7.32-7.40 (m, 12H), 7.08 (td, J= 7.2,4H), 7.00 (td, J=7.2,4H), 1.73 (s, 6H).
Embodiment 2
It is passed through nitrogen in 1L there-necked flask, sequentially adds 11.8g sodium tert-butoxide, 16.0g 9,9- dimethyl acridinium, in 20g Mesosome 1-5,400ml toluene, addition 69mg palladium acetate after stirring is completely dissolved to raw material, 0.3ml tri-tert-butylphosphine toluene solution, It is heated to return stirring reaction 12h, TLC monitoring compound 1-5 to completely consume, stops reaction, filtered after being down to 60~70 DEG C, filtered Liquid is washed till neutrality with hot water, and heat-insulation column is crossed after reflux water removal, and eluent concentration recrystallization obtains white solid 21.9g, i.e. compound 3, yield 78.5%.
The magnetic resonance spectroscopy data of compound 3:1H NMR (400MHz, CDCl3) δ 8.08 (d, J=7.6,1H), 7.68 (d, J =7.2,4H), 7.52 (td, J=7.6,2H), 7.46 (td, J=7.6,4H), 7.32-7.40 (m, 8H), 6.88 (d, J= 7.2,8H), 6.83 (td, J=7.2,4H), 6.54 (td, J=7.2,4H), 1.73 (s, 6H), 1.67 (s, 12H).
Embodiment 3
Synthesis step with intermediate 1-4, the difference is that, intermediate 1-3 is replaced with into intermediate 5-1, butyl lithium Dosage is 10.3ml, and the dosage of diphenyl phosphine chloride is 5.2g, and the dosage of hydrogen peroxide is 20ml, obtains the compound 8 of 17.5g, Yield 76.8%.
The magnetic resonance spectroscopy data of compound 8:1H NMR (400MHz, CDCl3) δ 8.13 (d, J=7.6,1H), 7.83 (s, 1H),7.65-7.68(m,3H),7.52-7.61(m,12H),7.40-7.46(m,8H),7.32-7.35(m,10H),7.08 (td, J=7.2,4H), 7.00 (td, J=7.2,4H), 1.73 (s, 6H).
Embodiment 4
Synthesis step with embodiment 1, the difference is that: the dosage of carbazole is 13.3g, and intermediate 1-5 is replaced with Mesosome 3-5, the dosage of potassium carbonate are 17.6g, and the dosage of 6 ether of 18- crown- is 0.84g, and the dosage of cuprous iodide is 0.61g, is obtained The compound 20 of 20.2g, yield 79.2%.
The magnetic resonance spectroscopy data of compound 20:1H NMR (400MHz, CDCl3) δ 7.67 (d, J=7.2,2H), 7.55 (d, ), J=7.2,4H 7.46-7.48 (m, 4H), 7.38-7.41 (m, 10H), 7.32-7.35 (m, 6H), 7.08-7.10 (d, J= 7.6,5H), 7.00 (td, J=7.2,4H).
Embodiment 5
Synthesis step with embodiment 1, the difference is that: the dosage of carbazole be 9.9g, intermediate 1-5 is replaced with into centre Body 4-2, the dosage of potassium carbonate are 13.1g, and the dosage of 6 ether of 18- crown- is 0.63g, and the dosage of cuprous iodide is 0.45g, is obtained The compound 54 of 17.3g, yield 71.8%.
The magnetic resonance spectroscopy data of compound 54:1H NMR (400MHz, CDCl3) δ 7.67 (d, J=7.2,2H), 7.49- 7.55 (m, 6H), 7.40-7.42 (m, 6H), 7.32 (d, J=7.2,2H), 7.08-7.12 (m, 5H), 7.00 (t, J=7.2, 4H), 6.80 (s, 4H), 3.12 (m, 6H), 1.29 (d, J=8.4,36H).
Embodiment 6
Synthesis step with intermediate 1-4 synthesis, the difference is that: intermediate 1-3 is replaced with into 20g intermediate 6-1, The dosage of butyl lithium is 10.6ml, and diphenyl phosphine chloride is replaced with 10.5g bis- (2,4,6- triisopropyl phenyl) boron fluoride, double Oxygen water consumption is 20ml, obtains the compound 55 of 19.2g, yield 68.2%.
The magnetic resonance spectroscopy data of compound 55:1H NMR (400MHz, CDCl3) δ 7.67 (d, J=7.2,2H), 7.53- 7.58 (m, 10H), 7.40-7.43 (m, 6H), 7.30-7.32 (m, 7H), 7.08 (td, J=7.2,4H), 7.00 (td, J= 7.2,4H), 6.80 (s, 4H), 3.12 (m, 6H), 1.29 (d, J=8.4,36H).
Embodiment 7
Synthesis step with embodiment 2, the difference is that: the dosage of sodium tert-butoxide be 8.8g, 9,9- dimethyl acridiniums Dosage is 12.0g, intermediate 1-5 is replaced with intermediate 2-2, the dosage of palladium acetate is 52mg, and the compound 56 of 18.5g is received Rate 71.5%.
The magnetic resonance spectroscopy data of compound 56:1H NMR (400MHz, CDCl3) δ 8.11 (d, J=7.6,1H), 7.82 (s, 1H), 7.62-7.67 (m, 3H), 7.46 (s, 1H), 7.40 (d, J=7.6,1H), 7.32 (d, J=7.2,2H), 6.80-6.88 (m, 12H), 6.54 (td, J=7.2,4H), 6.38 (d, J=7.2,4H), 3.12 (m, 6H), 1.73 (s, 6H), 1.67 (s, 12H), 1.29 (d, J=8.4,36H).
Embodiment 8
Synthesis step with embodiment 1, the difference is that: carbazole dosage be 9.6g, intermediate 1-5 is replaced with into intermediate 2-2, the dosage of potassium carbonate are 12.7g, and the dosage of 6 ether of 18- crown- is 0.61g, and the dosage of cuprous iodide is 0.44g, is obtained The compound 57 of 18.3g, yield 76.2%.
The magnetic resonance spectroscopy data of compound 57:1H NMR (400MHz, CDCl3) δ 8.11 (d, J=7.6,1H), 7.83 (s, 1H), 7.62-7.67 (m, 4H), 7.55 (d, J=7.2,4H), 7.40 (m, 5H), 7.32 (d, J=7.2,2H), 7.08 (td, J =7.2,4H), 7.00 (td, J=7.2,4H), 6.80 (s, 4H), 3.12 (m, 6H), 1.73 (s, 6H), 1.29 (d, J=8.4, 36H)。
We carry out T to the part of compounds and current material of the above embodiment of the present invention offer respectively1Energy level and HOMO, lumo energy test, the results are shown in Table 1:
1 the compounds of this invention T of table1Energy level and HOMO, LUMO
Note: highest molecule occupied orbital (HOMO) and the non-occupied orbital of minimum molecule (LUMO) and triplet energy state (T1) Simulation computed information is carried out for 09 software of Gaussian, calculation method uses B3LYP hydridization functional, base group 6-31g (d).
It can be obtained by table 1, compound provided by the invention has appropriate HOMO/LUMO, is conducive in OLED device The transmission of carrier and the transfer of energy, these compounds can be used as fluorescent host material use, can also be used as luminous material Material uses.In the case where no specific limitation, above-mentioned organic electroluminescence device can be fluorescent device or include heat Active delayed fluorescence (TADF) material devices.Therefore, the present invention is used for OLED device luminescent layer with indeno anthracene derivant compound Afterwards, the performances such as luminous efficiency and the service life of device can be effectively improved.
Below we just by taking part of compounds provided by the invention as an example, as emitting layer material (material of main part and/ Or dopant dye) be applied in organic electroluminescence device, to verify the excellent effect acquired by it.
Especially by the OLED material application that the present invention will be described in detail of the device performance of device embodiments 1~5 and comparative example 1 Excellent effect in the devices.Device embodiments 1~5 of the present invention are identical with the structure fabrication processes of comparative example 1, and adopt With identical glass substrate and electrode material, electrode material film thickness is also consistent, except that emitting layer material is done Adjustment, it is specific as follows.
Device Application Example
Device embodiments 1
A kind of organic electroluminescence device is present embodiments provided, structure is specific as shown in Figure 1, including stacking gradually to set Substrate 1, anode layer 2, hole injection layer 3, the first hole transmission layer 4, the second hole transmission layer 5, the luminescent layer 6, hole resistance set Barrier 7, electron transfer layer 8, electron injecting layer 9 and cathode layer 10.
Wherein, the selection of 2 material of anode layer has the indium tin oxide (ITO) of high official letter number, the selection of 3 material of hole injection layer HAT-CN, with a thickness of 5nm；First hole transmission layer, 4 material selects NPB, with a thickness of 60nm；The choosing of second hole transmission layer, 5 material TAPC is selected, with a thickness of 15nm；Luminescent layer 6 uses compound 1 as luminescent material, and Host1 adulterates mass ratio as material of main part It is 5%, with a thickness of 30nm；The material of hole blocking layer 7 selects TPBI, with a thickness of 10nm；The material of electron transfer layer 8 selects ET-1, with a thickness of 35nm；The material of electron injecting layer 9 selects Liq, with a thickness of 2nm；The material of cathode layer selects Al, with a thickness of 120nm。
Each used basic material structural formula of functional layer is as follows in device:
Specific preparation process is as follows for above-mentioned organic electroluminescence device:
1) ito anode on transparent glass substrate is cleaned, is respectively cleaned by ultrasonic 20 points with deionized water, acetone, ethyl alcohol respectively Then clock carries out plasma (Plasma) under oxygen atmosphere and handles 5 minutes；
2) on ito anode layer, hole injection layer material HAT-CN is deposited by vacuum evaporation mode, with a thickness of 5nm, this Layer is used as hole injection layer；
3) hole mobile material NPB is deposited by vacuum evaporation mode on hole injection layer, with a thickness of 60nm, which makees For the first hole transmission layer；
4) hole mobile material TAPC is deposited by vacuum evaporation mode on the first hole transmission layer NPB, with a thickness of 15nm, this layer is as the second hole transmission layer；
5) on the second hole transmission layer, luminescent layer is deposited by vacuum evaporation mode altogether, use compound 1 as shine Material, Host1 is as material of main part, and adulterating mass ratio is 5%, with a thickness of 30nm；
6) on luminescent layer, hole barrier materials TPBI is deposited by way of vacuum evaporation, with a thickness of 10nm, this Layer is used as hole blocking layer；
7) electron transport material ET-1 on the hole blocking layer, is deposited by way of vacuum evaporation, with a thickness of 35nm, this One layer is used as electron transfer layer；
8) electron injection material Liq on the electron transport layer, is deposited by way of vacuum evaporation, with a thickness of 2nm, this Layer is used as electron injecting layer；
9) on electron injecting layer, the evaporation cathode Al by way of vacuum evaporation, with a thickness of 120nm, the layer is as yin Pole conductive electrode uses.
Device embodiments 2
It is identical as device embodiments 1, difference: it regard compound 3 as dopant alternative compounds 1.
Device embodiments 3
It is identical as device embodiments 1, difference: it regard compound 8 as dopant alternative compounds 1.
Device embodiments 4
It is identical as device embodiments 1, difference: it regard compound 54 as dopant alternative compounds 1.
Device embodiments 5
It is identical as device embodiments 1, difference: it regard compound 55 as main body alternative compounds Host1, dopant is BD1。
Comparative example 1
Identical as device embodiments 1, difference: BD1 is as dopant.
Different components constituent prepared by device embodiments 1~4 of the present invention, comparative example 1, as shown in table 2:
The organic electroluminescence device constituent contrast table of each device embodiments of table 2
Cathode and anode are connected by each group organic electroluminescence device with well known driving circuit, pass through standard Method tests voltage-efficiency-current density relationship of OLED device using Keithley2400 power supply combination PR670 photometer； The service life of device is tested by constant flow method, and test condition is that constant current density is 10mA/cm2, test brightness decays to initially 80% time of brightness, as device LT80Service life, test result are as shown in table 3:
3 each group organic electroluminescence device results of property of table
As shown in Table 3, compound provided by the invention is applied to OLED as the material of main part and luminescent material of luminescent layer In photophore, function admirable.If the compound 1 in device embodiments 1 is used as luminescent material compared with comparative example 1BD1, shine effect Rate and service life have all obtained significant raising, and luminous efficiency improves 12.7%, and service life improves 30%；Such as device For compound 55 in embodiment 5 as material of main part compared with the Host1 in comparative example 1, luminous efficiency improves 12.7% left side The right side, service life improves 50%, and chromaticity coordinates is more excellent；It can be seen that selecting master of the compound of the present invention as OLED device Body material or luminescent material, the OLED luminescent device of comparison current material application, luminous efficiency, service life, excitation purity of device etc. Photoelectric properties have good performance, have very big application value and commercial promise using upper in OLED device, have good Good industrialization prospect.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art Mind 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 be also intended to include these modifications and variations.

Claims (10)

1. a kind of indeno anthracene derivant compound, which is characterized in that shown in its general structure such as following formula (I):
In formula (I), L1、L2、L3It is phenylene or substituted phenylene；Work as L1、L2、L3When for substituted phenylene, these are taken Dai Jiwei methyl, ethyl or cyano；N is the arbitrary integer between 0~3；
X is oxygen atom, sulphur atom, Si-m1m2、C-m1m2Or N-m3, in which: m1、m2It is respectively and independently selected from hydrogen atom, C1~C6 Alkyl, phenyl or xenyl；m3For aryl；
Ar1、Ar2It is electron donating group, is respectively and independently selected from substitution or unsubstituted carbazyl, formula (II), formula (III), formula (IV), group shown in formula (V), formula (VI) or formula (VII):
Work as Ar1、Ar2When being respectively and independently selected from substituted carbazyl, these substituent groups are alkyl, phenyl, the xenyl of C1~C6；
In formula (II), Ar3、Ar4It is respectively and independently selected from the substitution or unsubstituted aryl or fused ring aryl of C6~C30, C6~ The substitution of C30 or unsubstituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, substitution or unsubstituted amine Any one in base；
In formula (III), R1、R2It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, the alkoxy of C1~C6, cyano, trifluoromethyl Or it is fluorine-based；
R3、R4It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, the alkoxy of C1~C6, substitution or unsubstituted amido, The substitution of C6~C30 or unsubstituted condensed hetero ring group, five yuan, hexa-atomic heterocycle or substituted heterocycle, cyano, trifluoromethyl or It is fluorine-based；
In formula (IV), T is oxygen atom, sulphur atom, C-m4m5、Si-m4m5Or N-m6；
Wherein: m4、m5It is respectively and independently selected from hydrogen atom, the alkyl of C1~C6, phenyl or xenyl；
m6For the substitution of C6~C30 or unsubstituted aryl or fused ring aryl, the substitution of C6~C30 or unsubstituted thick miscellaneous Cyclic group, five yuan, hexa-atomic heterocycle or substituted heterocycle, replace or unsubstituted amido in any one；
In formula (V) and formula (VI), Y is carbon atom or silicon atom；
A is group shown in formula (VIII) or formula (Ⅸ):
Wherein, R5~R10It is the alkyl of C1~C6.
2. indeno anthracene derivant compound according to claim 1, which is characterized in that in the formula (II), Ar3、Ar4Point It is not independently selected from phenyl, xenyl, terphenyl, naphthalene, amido, carbazyl, furyl, dibenzofuran group, thienyl, two Benzothienyl, fluorenyl, dibenzopyridine base, dibenzo oxazines base or the mute piperazine base of pheno；
Work as Ar3、Ar4Be substituted when, substituent group be methyl, isopropyl, tert-butyl, methoxyl group, phenyl, cyano, xenyl, naphthalene, Amido, carbazyl, furyl, dibenzofuran group, thienyl, dibenzothiophene, fluorenyl, dibenzopyridine base, dibenzo One of oxazines base or the mute piperazine base of pheno.
3. indeno anthracene derivant compound according to claim 2, which is characterized in that group representated by the formula (II) Selected from one of following structural formula:
4. indeno anthracene derivant compound according to claim 1, which is characterized in that group representated by the formula (III) Selected from one of following structural formula:
5. indeno anthracene derivant compound according to claim 1, which is characterized in that in the formula (IV), m1、m2Respectively It is independently selected from hydrogen atom, methyl, ethyl, propyl, tert-butyl, phenyl, dibenzofuran group, dibenzothiophene, dibenzo pyrrole It is piperidinyl, dibenzo oxazines base, carbazyl, N- phenyl carbazole base, triphenylamine base, fluorenyl, any one in 9,9- dimethyl fluorenyl Kind；
m3Selected from phenyl, amido, xenyl, naphthalene, carbazyl, furyl, thienyl, fluorenyl, dibenzofuran group, dibenzo Thienyl, N- phenyl carbazole base, triphenylamine base, 9,9- dimethyl fluorenyl, dibenzofurans -4- base-(9,9- dimethyl -9H- Fluorenes -2- base)-amine, 3,9- diphenyl -9H- carbazyl, 3- dibenzofurans -4- base -9- phenyl -9H- carbazyl, 3- (9,9- bis- Methyl-9 H-fluorene -1- base) -9- phenyl -9H- carbazyl, 12,12- dimethyl -12H-10- oxa--indeno [2,1-B] fluorenyl, spiral shell Two fluorenyls.
6. indeno anthracene derivant compound according to claim 5, which is characterized in that group representated by the formula (IV) Selected from one of following structural formula:
7. indeno anthracene derivant compound according to claim 1, which is characterized in that be specially one in following compound Kind:
8. a kind of indeno anthracene derivant compound according to any one of claims 1 to 7 is in organic electroluminescence device Using.
9. a kind of organic electroluminescence device, including luminescent layer, which is characterized in that the emitting layer material includes claim 1 Indeno anthracene derivant compound described in any one of~7.
10. a kind of application of organic electroluminescence device as claimed in claim 9 in organic electroluminescence display device and method of manufacturing same.
CN201910399348.5A 2019-05-14 2019-05-14 Indenonanthracene derivative compound and application thereof Active CN110041366B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910399348.5A CN110041366B (en) 2019-05-14 2019-05-14 Indenonanthracene derivative compound and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910399348.5A CN110041366B (en) 2019-05-14 2019-05-14 Indenonanthracene derivative compound and application thereof

Publications (2)

Publication Number Publication Date
CN110041366A true CN110041366A (en) 2019-07-23
CN110041366B CN110041366B (en) 2022-02-18

Family

ID=67281893

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910399348.5A Active CN110041366B (en) 2019-05-14 2019-05-14 Indenonanthracene derivative compound and application thereof

Country Status (1)

Country Link
CN (1) CN110041366B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112479904A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN112479901A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN112538075A (en) * 2020-11-16 2021-03-23 南京高光半导体材料有限公司 Fused heterocyclic compound and organic electroluminescent device
CN113416175A (en) * 2021-05-31 2021-09-21 西安瑞联新材料股份有限公司 Compound with anthracene benzofuran as core skeleton and application thereof
CN114933578A (en) * 2022-06-08 2022-08-23 阜阳欣奕华材料科技有限公司 Anthracene furan compound, intermediate, organic electroluminescent device and display device
CN115417842A (en) * 2022-10-08 2022-12-02 陕西蒲城海泰新材料产业有限责任公司 Compound with anthracene benzofuran as core and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103187531A (en) * 2011-12-30 2013-07-03 昆山维信诺显示技术有限公司 Organic light-emitting device and purpose of double-polarity organic compound
CN107573206A (en) * 2017-09-12 2018-01-12 长春海谱润斯科技有限公司 A kind of organic compound and its synthetic method and organic luminescent device
CN108218663A (en) * 2016-12-15 2018-06-29 阜阳欣奕华材料科技有限公司 A kind of phenyl indene compounds, organic electroluminescence device and display device
CN108774258A (en) * 2018-09-10 2018-11-09 西安瑞联新材料股份有限公司 A kind of Heterocyclic Compound Containing Boron and its application in organic electro-optic device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103187531A (en) * 2011-12-30 2013-07-03 昆山维信诺显示技术有限公司 Organic light-emitting device and purpose of double-polarity organic compound
CN108218663A (en) * 2016-12-15 2018-06-29 阜阳欣奕华材料科技有限公司 A kind of phenyl indene compounds, organic electroluminescence device and display device
CN107573206A (en) * 2017-09-12 2018-01-12 长春海谱润斯科技有限公司 A kind of organic compound and its synthetic method and organic luminescent device
CN108774258A (en) * 2018-09-10 2018-11-09 西安瑞联新材料股份有限公司 A kind of Heterocyclic Compound Containing Boron and its application in organic electro-optic device

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112479904A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN112479901A (en) * 2019-09-11 2021-03-12 江苏三月光电科技有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN112479901B (en) * 2019-09-11 2023-04-07 江苏三月科技股份有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN112479904B (en) * 2019-09-11 2023-04-07 江苏三月科技股份有限公司 Organic compound with indeno-anthracene derivative as core and application thereof
CN112538075A (en) * 2020-11-16 2021-03-23 南京高光半导体材料有限公司 Fused heterocyclic compound and organic electroluminescent device
CN113416175A (en) * 2021-05-31 2021-09-21 西安瑞联新材料股份有限公司 Compound with anthracene benzofuran as core skeleton and application thereof
CN113416175B (en) * 2021-05-31 2023-04-18 西安瑞联新材料股份有限公司 Compound with anthracene benzofuran as core framework and application thereof
CN114933578A (en) * 2022-06-08 2022-08-23 阜阳欣奕华材料科技有限公司 Anthracene furan compound, intermediate, organic electroluminescent device and display device
CN114933578B (en) * 2022-06-08 2024-04-12 阜阳欣奕华材料科技有限公司 Anthraofuran compound, intermediate, organic electroluminescent device and display device
CN115417842A (en) * 2022-10-08 2022-12-02 陕西蒲城海泰新材料产业有限责任公司 Compound with anthracene benzofuran as core and application thereof

Also Published As

Publication number Publication date
CN110041366B (en) 2022-02-18

Similar Documents

Publication Publication Date Title
CN101331111B (en) New anthracene derivant, its preparation method and use the organic electronic light emitting device of this derivative
CN110041366A (en) A kind of indeno anthracene derivant compound and its application
CN102803437B (en) Compound for organic photoelectric device and organic photoelectric device including same
TWI461507B (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN109535131B (en) Compound taking cyanopyridine as receptor and application thereof
CN101668730B (en) Diamine derivative and use the organic electronic device of this derivant
CN109608453B (en) Compound taking 4, 7-phenanthroline as receptor and application thereof
CN108774258B (en) Boron-containing heterocyclic compound and application thereof in organic photoelectric device
KR20120011445A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20120009761A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN102933531A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN102958906A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN103228661A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20110119206A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
KR20110006915A (en) New compounds and organic electronic device using the same
CN111689962A (en) Compound with benzimidazole pyridine as receptor and application thereof
CN109053696B (en) Bipyrazine derivative and application thereof in organic photoelectric device
CN111606859A (en) Novel compound taking imidazole as receptor and application thereof
CN109970575A (en) Organic electroluminescent compounds and its preparation method and application
CN110964019B (en) Compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as receptor and application thereof
CN111454251A (en) Pyrazine derivative and application thereof in O L ED device
CN113416175B (en) Compound with anthracene benzofuran as core framework and application thereof
CN102675032B (en) 2,7-dianthracene base naphthalene compounds, luminescent layer material, organic electroluminescent device, display device and illuminator
CN111574505B (en) Compound with benzo [ c ] cinnoline as receptor and application thereof
CN108017648A (en) A kind of perimidine derivative and its 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
GR01 Patent grant
GR01 Patent grant