WO2020000921A1 - 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件 - Google Patents

一种蒽类有机发光化合物及其制备方法以及有机电致发光器件 Download PDF

Info

Publication number
WO2020000921A1
WO2020000921A1 PCT/CN2018/120966 CN2018120966W WO2020000921A1 WO 2020000921 A1 WO2020000921 A1 WO 2020000921A1 CN 2018120966 W CN2018120966 W CN 2018120966W WO 2020000921 A1 WO2020000921 A1 WO 2020000921A1
Authority
WO
WIPO (PCT)
Prior art keywords
anthracene
group
organic
organic light
substituted
Prior art date
Application number
PCT/CN2018/120966
Other languages
English (en)
French (fr)
Inventor
马晓宇
毕岩
刘琨
杨兵
王宏雷
李文军
王辉
Original Assignee
吉林奥来德光电材料股份有限公司
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 吉林奥来德光电材料股份有限公司 filed Critical 吉林奥来德光电材料股份有限公司
Publication of WO2020000921A1 publication Critical patent/WO2020000921A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • 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
    • C07D401/10—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 carbon chain containing aromatic rings
    • 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D403/10—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 carbon chain containing aromatic 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
    • C07D403/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—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
    • C07D409/10—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 carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • C07F9/65068—Five-membered rings having the nitrogen atoms in positions 1 and 3 condensed with carbocyclic rings or carbocyclic ring 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
    • 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
    • H10K85/40—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—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
    • H10K85/615—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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two 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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing 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
    • C09K2211/1088—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

Definitions

  • the present disclosure relates to the technical field of organic optoelectronic materials, in particular to an anthracene-based organic light-emitting compound, a preparation method thereof, and an organic electroluminescent device.
  • Organic electroluminescence refers to a light-emitting phenomenon in which organic materials directly convert electrical energy into light energy under the action of an electric field. It has the characteristics of self-illumination, bright colors, thin thickness, light weight, fast response speed, wide viewing angle, low driving voltage, resistance to harsh natural conditions, and can be made into flexible panels. It has gradually developed into the new generation of flat panel display. Advantage technology.
  • OELs organic light emitting diodes
  • a general organic electroluminescence device is composed of a cathode, an anode, and an organic substance layer therebetween.
  • the anode is transparent ITO
  • the cathode is composed of LiAl and the like.
  • the organic layer includes a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), and an electron Injection layer (EIL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EL light emitting layer
  • HBL hole blocking layer
  • ETL electron transport layer
  • EIL electron Injection layer
  • One side injects electrons from the cathode and the other side injects holes from the anode.
  • the injected electrons and holes are recombined in the light-emitting layer, and the electronic state changes from the ground state to the excited state. Because the excited state is extremely unstable, the excited state returns to a stable ground state. At this time, energy is released and manifests itself in the form of light.
  • the invention of the organic EL material Since the invention of the organic EL material, it has been widely used in the industry because of its obvious advantages over the previous two generations of display (CRT and LCD) devices. However, its development is restricted by factors such as its efficiency and longevity. In organic materials, the transfer speed of electrons and holes is different. If a suitable material is used, the electrons and holes can be efficiently transferred to the light-emitting layer, and the number of electrons and holes can be balanced to effectively improve the luminous efficiency.
  • Tris (8-hydroxyquinoline) aluminum (Alq3) has been used as an electron transporting material for nearly 30 years since its invention, and there is more data to prove that it is superior to conventional materials.
  • Alq3 Tris (8-hydroxyquinoline) aluminum
  • its application as an electron-transporting material restricts its movement to other layers. Therefore, the development of a new type of electron transmission material that meets the practical requirements has become an urgent need.
  • the technical problems to be solved by the present disclosure include, for example, providing an anthracene-based organic light-emitting compound, a preparation method thereof, and an organic electroluminescence device, which have high luminous efficiency and long life.
  • the anthracene-based organic light-emitting compound provided by the present invention has a structure represented by Formula I:
  • the anthracene-based organic light-emitting compound has a structure represented by Formula I-a:
  • R 1 and R 2 are independently preferably any one of the following groups:
  • C6 to C60 aryl C7 to C60 aralkyl, C8 to C60 arylalkenyl, C6 to C60 arylamine or C6 to C60 arylthiol, C2 to C60 heteroaryl, C10 to C60 fused ring group or C10 to C60 spiro ring group.
  • R 1 and R 2 are independently preferably: substituted or unsubstituted C3 to C30 cycloalkyl, C1 to C30 heterocyclyl, C6 to C30 aryl, C7 to C30 aryl An alkyl group, an arylamino group of C6 to C30 or an arylthiol group of C6 to C30, a heteroaryl group of C2 to C30, or a fused ring group of C10 to C30.
  • R 1 and R 2 are independently preferably: substituted or unsubstituted C3 to C20 cycloalkyl, C1 to C20 heterocyclyl, C6 to C20 aryl, C7 to C20 aryl An alkyl group, an arylamino group of C6 to C20 or an arylthiol group of C6 to C20, a heteroaryl group of C2 to C20, or a fused ring group of C10 to C20.
  • R 1 and R 2 are a triazinyl group and an anthryl group.
  • R 3 is preferably a substituted or unsubstituted C1-C60 alkyl group, a C3-C60 cycloalkyl group, a C1-C60 heterocyclic group, a C6-C60 aryl group, a C7-C60 aralkyl group, or a C8-C60 group.
  • R 3 is more preferably a substituted or unsubstituted C3 to C30 cycloalkyl group, a C1 to C30 heterocyclic group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, C2-C30 heteroaryl or C10-C30 fused ring group.
  • R 3 is more preferably a substituted or unsubstituted C3 to C20 cycloalkyl group, a C1 to C20 heterocyclic group, a C6 to C20 aryl group, a C7 to C20 aralkyl group, C2-C20 heteroaryl or C10-C20 fused ring group.
  • R 1 , R 2 and R 3 are independently preferably:
  • C6 to C60 aryl C7 to C60 aralkyl, C8 to C60 arylalkenyl, C6 to C60 arylamino or C6 to C60 arylthiol, C2 to C60 heteroaryl, C10 to C60 Fused ring group, C6-C60 aryl-substituted silicon group or C2-C60 heteroaryl-substituted silicon group.
  • the substituents of the above-mentioned substituted R 1 , R 2, and R 3 are independently halogen, cyano, nitro, hydroxyl, amino, sulfonate, sulfonyl, phosphate, or Phosphoryl
  • the substituents of the above-mentioned substituted R 1 , R 2, and R 3 are independently halogen, cyano, nitro, hydroxyl, amino, sulfonate, sulfonyl, phosphate, or Phosphoryl
  • C6 to C20 aryl C7 to C20 aralkyl, C8 to C20 arylalkenyl, C6 to C20 arylamino or C6 to C20 arylthiol, C2 to C20 heteroaryl, C10 to C20 Fused ring group, C6-C20 aryl-substituted silicon group or C2-C20 heteroaryl-substituted silicon group.
  • the substituents of the above-mentioned substituted R 1 , R 2, and R 3 are independently halogen, cyano, nitro, hydroxyl, amino, sulfonate, sulfonyl, phosphate, or Phosphoryl
  • R 1 , R 2 and R 3 are independently selected from any of the following groups:
  • Any one or more C atoms of the aforementioned cyclopentyl, cyclohexyl, phenyl, pyrrolyl, thienyl, or furyl groups may be substituted with O, S, N, or Si;
  • the H atom of the above-mentioned group or a substituted group may be deuterated.
  • substituted cyclopentyl, cyclohexyl, phenyl, pyrrolyl, thienyl or furyl substituents are preferably:
  • C6 to C60 aryl C7 to C60 aralkyl, C8 to C60 arylalkenyl, C6 to C60 arylamino or C6 to C60 arylthiol, C2 to C60 heteroaryl, C10 to C60 Fused ring group, C6-C60 aryl-substituted silicon group or C2-C60 heteroaryl-substituted silicon group.
  • the above-mentioned substituted cyclopentyl, cyclohexyl, phenyl, pyrrolyl, thienyl, or furyl substituents are preferably halogen, cyano, nitro, hydroxyl, amino, sulfo Acid, sulfonyl, phosphate or phosphoryl;
  • the above-mentioned substituted cyclopentyl, cyclohexyl, phenyl, pyrrolyl, thienyl, or furyl substituents are preferably halogen, cyano, nitro, hydroxyl, amino, sulfo Acid, sulfonyl, phosphate or phosphoryl;
  • C6 to C20 aryl C7 to C20 aralkyl, C8 to C20 arylalkenyl, C6 to C20 arylamino or C6 to C20 arylthiol, C2 to C20 heteroaryl, C10 to C20 Fused ring group, C6-C20 aryl-substituted silicon group or C2-C20 heteroaryl-substituted silicon group.
  • the above-mentioned substituted cyclopentyl, cyclohexyl, phenyl, pyrrolyl, thienyl, or furyl substituents are preferably halogen, cyano, nitro, hydroxyl, amino, sulfo Acid, sulfonyl, phosphate or phosphoryl;
  • the R 1 , R 2 and R 3 are independently preferably any one of the following groups, or a group formed by connecting two or more arbitrary groups by a single bond:
  • X and Y are independently preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C30 alkyl group, a C3-C30 cycloalkyl group, or a C1-C30 alkyl group.
  • they are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 alkoxy group, and a C2-C20 group.
  • they are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C10 alkyl group, a C3-C12 cycloalkyl group, a C1-C10 alkoxy group, and a C2-C10 group.
  • the Q is C or N.
  • the P is C, N, O or S.
  • the Z is O or S.
  • the position of the single bond connection is not particularly limited in the present disclosure, and is not limited to the connection position marked by the above curved line, and may be a C atom and a C atom , C atom and heteroatom or any connection between heteroatom and heteroatom.
  • the anthracene-based organic light-emitting compound has the following specific structure:
  • the single bond in the structural formula of the above compound represents a methyl group.
  • the present disclosure also provides a method for preparing the anthracene-based organic light-emitting compound, including the following steps:
  • R 1 , R 2, and R 3 are the same as above, and will not be repeated here.
  • the preparation method specifically includes the following steps:
  • Step 1 Tris (dibenzylideneacetone) dipalladium and tricyclohexylphosphine are added to a dry 1,4-dioxane solvent and activated at room temperature for a period of time. To the reaction solution were added intermediate 1-a, pinacol diborate, and potassium acetate. The reaction solution was heated to react.
  • Step 2 Add 2-bromoanthracene, formula 2-a, and acid binding agent to a mixed solvent of toluene / ethanol / water (preferably 3: 1: 1 by volume). The air was replaced with nitrogen three times, tetrakis (triphenylphosphine) palladium was added, and the air was replaced three times with nitrogen again, and the reaction was heated under the protection of nitrogen.
  • a mixed solvent of toluene / ethanol / water preferably 3: 1: 1 by volume.
  • the catalyst is removed using diatomaceous earth, the liquid is separated, the organic phase is retained, and the reduced amount is distilled under reduced pressure.
  • Step 3 Add intermediate 2-b to DMF solvent, add NBS, and heat the reaction solution.
  • reaction solution is preferably concentrated to a small amount and added dropwise to petroleum ether to precipitate. After the solid is completely precipitated, suction filtration and drying are performed to obtain the intermediate as shown in Formula III;
  • Step 4 Add intermediate formula III, the compound represented by formula II, and potassium carbonate to 300 ml of a mixed solvent of toluene / ethanol / water (preferably 3: 1: 1 by volume). The air was replaced with nitrogen three times, and tetrakis (triphenylphosphine) palladium was added, and the reaction was heated under the protection of nitrogen.
  • a mixed solvent of toluene / ethanol / water preferably 3: 1: 1 by volume.
  • the catalyst is preferably removed using diatomaceous earth. Separate the liquid, keep the organic phase, and distill at least the amount under reduced pressure.
  • Step 5 Add intermediate formula IV to DMF solvent, add NBS, and heat the reaction solution.
  • Step 6 Add intermediate formula V, R 1 -B (OH) 2 and potassium carbonate to a mixed solvent of toluene / ethanol / water (preferably 3: 1: 1 by volume). Tetrakis (triphenylphosphine) palladium was added, and the mixture was heated to 90 ° C under a nitrogen atmosphere and reacted for 12 hours.
  • the catalyst is preferably removed using diatomaceous earth. Separate the liquid, keep the organic phase, and distill at least the amount under reduced pressure.
  • the present disclosure provides an organic electroluminescent device including the above-mentioned anthracene-based organic light-emitting compound or the anthracene-based organic light-emitting compound prepared by the above-mentioned preparation method.
  • the organic electroluminescence device may be an organic electroluminescence device well known to those skilled in the art, and the present disclosure preferably includes a first electrode, a second electrode, and one or more provided between the first electrode and the second electrode. Multiple organic layers; at least one of the organic layers includes the anthracene-based organic light-emitting compound.
  • the organic layer refers to all layers between the first electrode and the second electrode of the organic electroluminescent device. At least one of the organic substance layers is a light emitting layer.
  • the organic layer preferably includes a hole injection layer, a hole transport layer, a hole injection and hole transport skill layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection.
  • Layer and one or more of layers having both electron transport and electron injection skills and more preferably includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron transport layer which are disposed in this order.
  • an electron injection layer, or a hole injection and hole transport skill layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and a layer having both electron transport and electron injection skills are disposed in this order.
  • the organic substance layer of the present disclosure includes a hole injection layer, a hole transport layer, and a layer having both hole injection and hole transport skills
  • the hole injection layer, the hole transport layer, and both hole injection and holes are preferably provided.
  • At least one of the transport skill layers includes a hole injection substance, a hole transport substance, or a substance having both hole injection and hole transport skills.
  • the organic substance layer of the present disclosure has a single-layer structure
  • the organic substance layer is a light-emitting layer
  • the organic substance layer includes a light-emitting layer
  • the light-emitting layer preferably includes a phosphorescent host and a fluorescent host.
  • phosphorescent doped materials and fluorescent doped materials are examples of phosphorescent doped materials.
  • the electron transport layer may include an anthracene-based organic light-emitting compound represented by formula (I).
  • the electron transport layer further includes a metal compound.
  • the metal compound may be any substance known to those skilled in the art for electron transport, and is not particularly limited.
  • the organic substance layer includes both a light emitting layer and an electron transporting layer
  • the light emitting layer and the electron transporting layer may each include an anthracene-based organic light emitting compound represented by formula (I) having the same or different structure.
  • the organic electroluminescent device provided by the present disclosure may be made by using an anthracene-based organic light-emitting compound represented by formula (I) and a conventional material.
  • the present disclosure does not limit the method for preparing the organic electroluminescent device, and the art The conventional method is sufficient.
  • the present disclosure preferably uses a method such as thin film evaporation, electron beam evaporation, or physical vapor deposition to vapor-deposit a metal and a conductive oxide and an alloy thereof on a substrate to form an anode, and then an organic layer and The cathode was evaporated to obtain an organic electroluminescent device.
  • the organic layer may include the above-mentioned multilayer structures of the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron transport layer, and these multilayer structures may be deposited according to the thin film and electron beam evaporation described above. Or physical vapor deposition, etc., a variety of polymer material solvent engineering can also be used instead of evaporation methods, such as spin-coating, tape-casting, doctor-blading ), Screen printing (Screen-Printing), inkjet printing or thermal-imaging (Thermal-Imaging) and other methods to reduce the number of layers of manufacturing.
  • evaporation methods such as spin-coating, tape-casting, doctor-blading ), Screen printing (Screen-Printing), inkjet printing or thermal-imaging (Thermal-Imaging) and other methods to reduce the number of layers of manufacturing.
  • the organic electroluminescence device provided by the present disclosure can also be divided into front light emission, back light emission, or both light emission according to the materials used; and the organic electroluminescence device can be applied to organic light emitting devices (OLED) and organic solar cells (OSC) in the same principle. ), Electronic paper (e-paper), organic photoreceptor (OPC) or organic thin film transistor (OTFT).
  • OLED organic light emitting devices
  • OSC organic solar cells
  • the anthracene-based organic light-emitting compound represented by the formula (I) provided in the present disclosure can also be applied in accordance with a principle applicable to organic light-emitting devices in organic devices such as organic solar cells, OLEDs for lighting, flexible OLEDs, organic photoreceptors, and organic transistors.
  • the present disclosure also provides an organic optoelectronic material including an anthracene-based organic light-emitting compound represented by the above formula (I); the organic optoelectronic material includes an organic solar cell, an electronic paper, an organic photoreceptor, or an organic transistor.
  • the present disclosure provides an anthracene-based organic light-emitting compound having a structure represented by Formula I.
  • the novel anthracene-based organic light-emitting compounds provided by the present disclosure are used as materials for the electron transporting layer of the organic electroluminescent device, and the luminous efficiency is significantly improved, and the lifetime is significantly improved.
  • the anthracene organic light-emitting compound has a short synthetic route, simple process, high yield, easy-to-obtain raw materials, mild reaction conditions, and low cost, and is suitable for industrial production.
  • anthracene-based organic light-emitting compound provided by the present disclosure a preparation method thereof, and an organic electroluminescent device are described in detail below with reference to examples.
  • Reaction process Add intermediate D-1 (16.6g, 49.8mmol), G-1 (19.0g, 49.8mmol), and potassium carbonate (20.6g, 149.4mmol) to 300ml toluene / ethanol / water (volume ratio 3: 1: 1) in a mixed solvent. The air was replaced with nitrogen three times, and tetrakis (triphenylphosphine) palladium (0.58 g, 0.5 mmol) was added. The air was replaced with nitrogen three times, and heated to 90 ° C. under the protection of nitrogen.
  • Reaction process Add intermediate I-1 (19.5g, 32.42mmol), phenylboronic acid (5.92g, 48.63mmol), potassium carbonate (13.4g, 97.26mmol) to 500ml toluene / ethanol / water (volume ratio 3: 1 : 1) in a mixed solvent. The air was replaced with nitrogen three times, and tetrakis (triphenylphosphine) palladium (0.49 g, 0.32 mmol) was added. The air was replaced with nitrogen three times, and heated to 90 ° C. under the protection of nitrogen.
  • the Fisher coating thickness is The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, repeatedly washed with distilled water twice, and ultrasonically washed for 10 minutes. After the distilled water was cleaned, the solvents such as isopropanol, acetone, and methanol were sequentially washed and dried, The substrate was transferred to a plasma cleaner, and the substrate was washed for 5 minutes and sent to a vapor deposition machine. As a hole injection layer, 4,4 ', 4 "-tri [2-naphthylphenylamino] triphenylamine (2-TNATA) with a thickness of 50 nm was deposited on the prepared ITO transparent electrode.
  • N'-bis (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine with a thickness of 30 nm was vacuum deposited on the hole injection layer (a-NPD) is used as a hole transport layer. Then, a blue host material 9,10-bis (2-naphthyl) anthracene (AND) and a doping material N1 are deposited on the hole transport layer to a thickness of 30 nm.
  • a double (10nm) double ( 2-Methyl-8-hydroxyquinoline-N1,08)-(1,1'-biphenyl-4-hydroxy) aluminum (BAlq) was used as a hole blocking layer.
  • the thickness was vacuum-evaporated on the hole blocking layer.
  • Any of the compounds of the present disclosure prepared as shown in Table 6 at 40 nm was used as an electron transport layer.
  • Lithium fluoride (LiF) having a thickness of 0.5 nm was vacuum-evaporated on the electron transport layer as an electron injection layer.
  • 150 nm of aluminum was evaporated as a cathode to complete the preparation of the organic electroluminescent device.
  • a forward DC bias voltage was applied to the organic electroluminescence device prepared above, and the organic electroluminescence characteristics were measured using a PR-650 photometric device from Photo Research, and a reference gray scale of 5000 cd / m 2 was used from McScience.
  • the life measuring device measured the life of T95. The results are shown in Table 7.
  • An organic electroluminescent device was prepared in the same manner as in Example 7.
  • the structure of the compound of the electron transport layer was as follows:
  • the prepared organic electroluminescent device was tested in the same manner as in Example 7, and the results are shown in Table 7.
  • the present disclosure provides an anthracene-based organic light-emitting compound having a structure represented by Formula I.
  • the novel anthracene-based organic light-emitting compounds provided by the present disclosure are used as materials for the electron transporting layer of the organic electroluminescent device, and the luminous efficiency is significantly improved, and the lifetime is significantly improved.
  • the anthracene organic light-emitting compound has a short synthetic route, simple process, high yield, easy-to-obtain raw materials, mild reaction conditions, and low cost, and is suitable for industrial production.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本公开提供了一种蒽类有机发光化合物，具有式Ⅰ所示结构。本公开提供的新型蒽类有机发光化合物作为有机电致发光器件的电子传输层材料，与其他电子传输层材料相比，发光效率提升明显，寿命改善显著。且所述蒽类有机发光化合物合成路线较短，工艺简单，产率高，原料易得，反应条件温和，成本低，适合工业化生产。

Description

一种蒽类有机发光化合物及其制备方法以及有机电致发光器件
相关申请的交叉引用
本申请要求于2018年6月28日提交中国国家知识产权局的申请号为2018106912485、名称为“一种蒽类有机发光化合物及其制备方法以及有机电致发光器件”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本公开涉及有机光电材料技术领域，尤其涉及一种蒽类有机发光化合物及其制备方法以及有机电致发光器件。
背景技术
有机电致发光(EL)是指有机材料在电场作用下，将电能直接转化为光能的一种发光现象。其具有自发光、颜色鲜艳亮丽、厚度薄、质量轻、响应速度快、视角广、驱动电压低、耐受苛刻自然条件、可做成柔性面板等特点，逐渐发展成为新一代平板显示领域最具优势技术。
关于有机电致发光器件(OEL)即有机发光二极管(OLED)的研究起始于上世纪50年代。一般的有机电致发光器件是由阴极、阳极和位于二者之间的有机物层构成的。一般阳极为透明ITO，阴极由LiAl等组成。其中的有机层包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、发光层(EL)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)。两个电极之间形成电压，一边从阴极注入电子，另一边从阳极注入空穴，注入的电子和空穴在发光层再结合，其电子状态从基态转向激发态。因为激发态极其不稳定，激发态又回到稳定的基态。这时，能量被释放，表现为光的形式。
有机EL材料自发明以来，因其相对于前两代显示(CRT以及LCD)器具有明显的优势，被产业广泛的应用。但因其效率以及寿命等因素制约了其发展。在有机材料中，电子和空穴的转移速度是不同的，若使用适合的材料，将电子和空穴有效的转移到发光层，平衡电子和空穴的数量，可有效的提高发光效率。
随着市场对有机EL器件要求不断的提高，具有高效率、长寿命的器件成为了发展趋势。然而适合的材料十分难于寻找。三(8-羟基喹啉)铝(Alq3)作为电子传输材料自发明以来使用了将近30年，而且有较多的资料证明其比常规材料优异。但其作为电子传输材料，有向其他层移动等因素制约了其应用。因此开发一种符合实用性要求的新型电子传输材料成为了迫切需求。
发明内容
有鉴于此，本公开要解决的技术问题包括例如提供一种蒽类有机发光化合物及其制备方法以及有机电致发光器件，具有较高的发光效率和寿命。
本发明提供的蒽类有机发光化合物，具有式Ⅰ所示结构：
Figure PCTCN2018120966-appb-000001
在本公开的一些具体实施例中，所述蒽类有机发光化合物具有式Ⅰ-a所示结构：
Figure PCTCN2018120966-appb-000002
其中，R 1和R 2独立地优选为以下任一基团：
氢、卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
取代或非取代的硅基、硼烷基或磷基；
取代或非取代的C1～C60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
取代或非取代的C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基。
在一种或多种实施方式中，R 1和R 2独立地优选为：取代或非取代的C3～C30环烷基、C1～C30杂环基、C6～C30芳基、C7～C30的芳烷基、C6～C30的芳胺基或C6～C30的芳巯基、C2～C30的杂芳基或C10～C30的稠环基。
在一种或多种实施方式中，R 1和R 2独立地优选为：取代或非取代的C3～C20环烷基、C1～C20杂环基、C6～C20芳基、C7～C20的芳烷基、C6～C20的芳胺基或C6～C20的芳巯基、C2～C20的杂芳基或C10～C20的稠环基。
本公开中，所述R 1和R 2均不为三嗪基和蒽基。
R 3优选为取代或非取代的C1～C60的烷基、C3～C60的环烷基、C1～C60的杂环基、C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基。
在一种或多种实施方式中，R 3更优选为取代或非取代的C3～C30的环烷基、C1～C30的杂环基、C6～C30芳基、C7～C30的芳烷基、C2～C30的杂芳基或C10～C30的稠环基。
在一种或多种实施方式中，R 3更优选为取代或非取代的C3～C20的环烷基、C1～C20的杂环基、C6～C20芳基、C7～C20的芳烷基、C2～C20的杂芳基或C10～C20的稠环基。
上述取代的R 1、R 2和R 3的取代基团独立地优选为：
卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
C6～C60的芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基、C6～C60芳基取代的硅基或C2～C60杂芳基取代的硅基。
在一种或多种实施方式中，上述取代的R 1、R 2和R 3的取代基团独立地为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～30的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C30的环烷基；
C6～C30的芳基、C7～C30的芳烷基、C8～C30的芳烯基、C6～C30的芳胺基或C6～C30的芳巯基、C2～C30的杂芳基、C10～C30的稠环基、C6～C30芳基取代的硅基或C2～C30杂芳基取代的硅基。
在一种或多种实施方式中，上述取代的R 1、R 2和R 3的取代基团独立地为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～20的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C20的环烷基；
C6～C20的芳基、C7～C20的芳烷基、C8～C20的芳烯基、C6～C20的芳胺基或C6～C20的芳巯基、C2～C20的杂芳基、C10～C20的稠环基、C6～C20芳基取代的硅基或C2～C20杂芳基取代的硅基。
在一种或多种实施方式中，上述取代的R 1、R 2和R 3的取代基团独立地为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～10的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C12的环烷基；
C6～C12的芳基、C7～C12的芳烷基、C8～C14的芳烯基、C6～C12的芳胺基或C6～C12的芳巯基、C2～C12的杂芳基、C10～C20的稠环基、C6～C12芳基取代的硅基或C2～C12杂芳基取代的硅基。
在本公开的一些具体实施例中，所述R 1、R 2和R 3独立地选自以下任一基团：
取代或非取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基；
或者2～6个任意以上基团稠合形成的稠环基团；
或者2～6个任意以上基团通过单键、N、O、B、Si、P、P＝O、S或S＝O连接形成的基团；
上述环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的任意一个或多个C原子可被O、S、N或Si取代；
上述基团或取代基团的H原子可被氘代。
上述取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的取代基团优选为：
卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
C6～C60的芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基、C6～C60芳基取代的硅基或C2～C60杂芳基取代的硅基。
在一种或多种实施方式中，上述取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的取代基团优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～30的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C30的环烷基；
C6～C30的芳基、C7～C30的芳烷基、C8～C30的芳烯基、C6～C30的芳胺基或C6～C30的芳巯基、C2～C30的杂芳基、C10～C30的稠环基、C6～C30芳基取代的硅基或C2～C30杂芳基取代的硅基。
在一种或多种实施方式中，上述取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的取代基团优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～20的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C20的环烷基；
C6～C20的芳基、C7～C20的芳烷基、C8～C20的芳烯基、C6～C20的芳胺基或C6～C20的芳巯基、C2～C20的杂芳基、C10～C20的稠环基、C6～C20芳基取代的硅基或C2～C20杂芳基取代的硅基。
在一种或多种实施方式中，上述取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的取代基团优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～10的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C12的环烷基；
C6～C12的芳基、C7～C12的芳烷基、C8～C14的芳烯基、C6～C12的芳胺基或C6～C12的芳巯基、C2～C12的杂芳基、C10～C20的稠环基、C6～C12芳基取代的硅基或C2～C12杂芳基取代的硅基。
在本公开的另外一些具体实施例中，所述R 1、R 2和R 3独立地优选为以下任一基团，或者2个以上任意基团由单键连接形成的基团：
Figure PCTCN2018120966-appb-000003
其中，X和Y独立地优选为氢原子、卤素原子、氰基、硝基、羟基、氨基、取代或未取代的C1～C30的烷基、C3～C30的环烷基、C1～C30的烷氧基、C2～C30的烯基、C7～C30的烷芳基、C7～C30的烷芳氧基、C6～C30的芳基、C6～C30的芳氧基、C2～C30的杂环基、C5～C30的杂芳基或C6～C30的芳香族胺；
更优选为氢原子、卤素原子、氰基、硝基、羟基、氨基、取代或未取代的C1～C20的烷基、C3～C20的环烷基、C1～C20的烷氧基、C2～C20的烯基、C7～C20的烷芳基、C7～C20的烷芳氧基、C6～C20的芳基、C6～C20的芳氧基、C2～C20的杂环基、C5～C20的杂芳基或C6～C20的芳香族胺。
更优选为氢原子、卤素原子、氰基、硝基、羟基、氨基、取代或未取代的C1～C10的烷基、C3～C12的环烷基、C1～C10的烷氧基、C2～C10的烯基、C7～C20的烷芳基、C7～C20的烷芳氧基、C6～C20的芳基、C6～C20的芳氧基、C2～C12的杂环基、C5～C20的杂芳基或C6～C20的芳香族胺。
所述Q为C或N。
所述P为C、N、O或S。
所述Z为O或S。
上述取代基结构式中的弯线表示连接位置。
当上述2个以上任意基团由单键连接形成基团时，本公开对单键连接的位置并无特殊限定，也并不局限于上述弯线标注的连接位置，可以为C原子与C原子，C原子与杂原子或杂原子与杂原子之间的任意连接。
在本公开的另外一些具体实施例中，所述蒽类有机发光化合物具有以下具体结构：
Figure PCTCN2018120966-appb-000004
Figure PCTCN2018120966-appb-000005
Figure PCTCN2018120966-appb-000006
Figure PCTCN2018120966-appb-000007
Figure PCTCN2018120966-appb-000008
Figure PCTCN2018120966-appb-000009
上述化合物结构式中的单键表示甲基。
本公开还提供了上述蒽类有机发光化合物的制备方法，包括以下步骤：
式Ⅱ所示化合物和式Ⅲ所示化合物进行缩合反应，得到式Ⅳ所示化合物；
式Ⅳ所示化合物经溴化，得到式Ⅴ所示化合物；
式Ⅴ所示化合物和R 1-B(OH) 2反应，得到式Ⅰ所示化合物；
Figure PCTCN2018120966-appb-000010
上述R 1、R 2和R 3的范围同上，在此不再赘述。
上述反应的反应路线如下：
Figure PCTCN2018120966-appb-000011
在本公开的一些具体实施例中，所述制备方法具体包括以下步骤：
步骤1：将三(二亚苄基丙酮)二钯和三环己基膦加入到干燥的1,4-二氧六环溶剂中，在室温下活化一段时间。向反应液中加入中间体1-a、联硼酸频那醇酯以及醋酸钾。将反应液加热反应。
反应结束后，优选的，利用硅藻土除去盐以及催化剂，减压蒸馏滤液至少许，滴加至石油醚中析出。 待固体析出完全，抽滤、烘干，得到中间体如式Ⅱ所示。
Figure PCTCN2018120966-appb-000012
步骤2：将2-溴蒽、式2-a、缚酸剂加入到甲苯/乙醇/水(体积比优选3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基膦)钯，再次用氮气置换空气三次，在氮气保护下加热反应。
待反应结束后，优选的，使用硅藻土除去催化剂，分液，保留有机相，减压蒸馏至少量。将所得粗品使用柱层析色谱进行分离(洗脱剂优选DCM:PE＝1:5)得到中间体。
Figure PCTCN2018120966-appb-000013
步骤3：将中间体2-b加入到DMF溶剂中，加入NBS，将反应液加热反应。
反应结束后，优选的，将反应液浓缩至少许，滴加至石油醚中析出。待固体析出完全，抽滤，烘干，得到中间体如式Ⅲ所示；
Figure PCTCN2018120966-appb-000014
步骤4：将中间体式Ⅲ、与式Ⅱ所示化合物、碳酸钾加入到300ml甲苯/乙醇/水(体积比优选3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基膦)钯，在氮气保护下加热反应。
反应结束后，优选的，使用硅藻土除去催化剂。分液，保留有机相，减压蒸馏至少量。将所得粗品使用柱层析色谱进行分离(洗脱剂优选DCM:PE＝1:10)得到中间体如式Ⅳ所示；
Figure PCTCN2018120966-appb-000015
步骤5：将中间体式Ⅳ加入到DMF溶剂中，加入NBS，将反应液加热反应。
反应结束后，优选的，减压蒸馏至少许溶液，滴加至石油醚中析出。待固体析出完全，抽滤，烘干，得到中间体如式Ⅴ所示。
Figure PCTCN2018120966-appb-000016
步骤6：将中间体式Ⅴ、R 1-B(OH) 2、碳酸钾加入到甲苯/乙醇/水(体积比优选3:1:1)的混合溶剂中。加入四(三苯基膦)钯，在氮气保护下加热到90℃,反应12h。
反应结束后，优选的，使用硅藻土除去催化剂。分液，保留有机相，减压蒸馏至少量。将所得粗品使用柱层析色谱进行分离(洗脱剂优选DCM:PE＝1:5)，得到式Ⅰ所示目标化合物；
Figure PCTCN2018120966-appb-000017
本公开提供了一种有机电致发光器件，包括上述蒽类有机发光化合物或上述制备方法制备的蒽类有机发光化合物。
所述有机电致发光器件为本领域技术人员熟知的有机电致发光器件即可，本公开优选包括第一电极、第二电极和设置于所述第一电极与第二电极之间的一个或多个有机物层；至少一个所述有机物层包含上述蒽类有机发光化合物。
本公开中，所述有机物层是指有机电致发光器件第一电极和第二电极之间的全部层。所述有机物层中的至少一层为发光层。
按照本公开，所述有机物层优选包括空穴注入层、空穴传输层、同时具备空穴注入和空穴传输技能层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层与同时具备电子传输和电子注入技能层中的一层或多层，更优选包括依次设置的空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层与电子注入层或依次设置的既具备空穴注入又具备空穴传输技能层、电子阻挡层、发光层、空穴阻挡层与既具备电子传输又具备电子注入技能层。
当本公开有机物层包含空穴注入层、空穴传输层和同时具备空穴注入和空穴传输技能层时，优选所述空穴注入层、空穴传输层和同时具备空穴注入和空穴传输技能层中至少一层包含空穴注入物质、空穴传输物质或既具备空穴注入又具备空穴传输技能的物质。
当本公开有机物层为单层结构时，所述有机物层为发光层，当所述有机物层为多层结构时，所述有机物层包括发光层；所述发光层中优选包括磷光主体、荧光主体、磷光掺杂材料与荧光掺杂材料中的一种或多种。
当所述有机物层包括电子传输层时，所述电子传输层可包括式(I)所示的蒽类有机发光化合物。在本公开的一些具体实施例中，所述电子传输层还包括金属化合物。所述金属化合物为本领域技术人员熟知的用于电子传输的物质即可，并无特殊的限制。
当所述有机物层同时包括发光层与电子传输层时，所述发光层与电子传输层可分别包括结构相同或不相同的式(I)所示的蒽类有机发光化合物。
本公开提供的有机电致发光器件，利用式(I)所示的蒽类有机发光化合物及常规材料制成即可，本公开对所述有机电致发光器件的制备方法并无限定，本领域常规方法即可，本公开优选利用薄膜蒸镀、电子束蒸发或物理气相沉积等方法在基板上蒸镀金属及具有导电性的氧化物及它们的合金形成阳极，然后在其上形成有机物层及蒸镀阴极，得到有机电致发光器件。
所述有机物层可以同时包括上述的空穴注入层、空穴传输层、发光层、空穴阻挡层及电子传输层的多层结构，并且这些多层结构可按照上述薄膜蒸镀、电子束蒸发或物理气相沉积等方法蒸镀，也可使用 多样的高分子材料溶剂工程替代蒸镀方法，如旋转涂膜(spin-coating)、薄带成型(tape-casting)、刮片法(doctor-blading)、丝网印刷(Screen-Printing)、喷墨印刷或热成像(Thermal-Imaging)等方法减少层数制造。
本公开提供的有机电致发光器件按照使用的材料也可分为前面发光、背面发光或两面发光；并且该有机电致发光器件可以同样原理应用在有机发光器件(OLED)、有机太阳电池(OSC)、电子纸(e-paper)、有机感光体(OPC)或有机薄膜晶体管(OTFT)上。
本公开提供的式(I)所示的蒽类有机发光化合物在有机太阳电池、照明用OLED、柔性OLED、有机感光体及有机晶体管等有机器件中也可按照适用有机发光器件的原理适用。
本公开还提供了一种有机光电材料，包括上述式(I)所示的蒽类有机发光化合物；所述有机光电材料包括有机太阳电池、电子纸、有机感光体或有机晶体管。
与现有技术相比，本公开提供了一种蒽类有机发光化合物，具有式Ⅰ所示结构。本公开提供的新型蒽类有机发光化合物作为有机电致发光器件的电子传输层材料，与其他电子传输层材料相比，发光效率提升明显，寿命改善显著。且所述蒽类有机发光化合物合成路线较短，工艺简单，产率高，原料易得，反应条件温和，成本低，适合工业化生产。
具体实施方式
为了进一步说明本公开，下面结合实施例对本公开提供的蒽类有机发光化合物及其制备方法以及有机电致发光器件进行详细描述。
实施例1
中间体C-1的合成：
Figure PCTCN2018120966-appb-000018
反应过程：将2-溴蒽(20.0g，77.8mmol)、苯硼酸(11.38g，93.34mmol)、碳酸钾(32.25g，233.34mmol)加入到500ml甲苯/乙醇/水(体积比3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基膦)钯(0.9g，0.78mmol)，再次用氮气置换空气三次，在氮气保护下加热到90℃。
处理过程：TLC监测。待反应结束后，在氮气保护下冷却至室温。使用分液漏斗进行分液，保留有机相。使用硅藻土除去催化剂，用DCM洗硅藻土至无产品。浓缩滤液至少量，硅胶拌样，使用硅胶漏斗进行分离(DCM:PE＝1:5)得到中间体C-1(16.81g，收率＝85％)。
按照上述方法制备得到表1所示中间体。
表1实施例1反应原料以及产物结构及表征汇总
Figure PCTCN2018120966-appb-000019
Figure PCTCN2018120966-appb-000020
实施例2
中间体D-1的合成
Figure PCTCN2018120966-appb-000021
反应过程：将中间体C-1(16.5g，64.88mmol)加入到200ml DMF溶剂中，加入NBS(13.86g，77.86mmol)，将反应液加热到50℃。
处理过程：TLC监测反应。反应结束后，将反应液浓缩至少许，缓慢滴加到搅拌的石油醚中。待固体析出完全，抽滤，烘干，得到中间体D-1(19.45g，收率＝90％)。
按照上述方法制备得到表2所示中间体。
表2实施例2反应原料以及产物结构及表征汇总
Figure PCTCN2018120966-appb-000022
Figure PCTCN2018120966-appb-000023
实施例3
中间体G-1的合成
Figure PCTCN2018120966-appb-000024
反应过程：将三(二亚苄基丙酮)二钯(1.05g，1.145mmol)和三环己基膦(0.8g，2.86mmol)加入到干燥的1,4-二氧六环溶剂中，用氮气置换空气三次，在室温下活化30分钟。向反应液中加入E-1(20.0g，57.27mmol)、联硼酸频那醇酯(17.45g，68.724mmol)以及醋酸钾(22.45g，229.08mmol)。用氮气置换空气三次，将反应液加热到100℃。
处理过程：TLC监测反应。反应结束后，在氮气保护下冷却至室温。利用硅藻土除去催化剂，用二氯甲烷冲洗滤饼至无产品。浓缩滤液至少许，边搅拌将将浓缩液滴加至石油醚中。待固体析出完全，抽滤、烘干，得到中间体G-1(19.06g，收率84％)。
按照上述方法制备得到表3所示中间体。
表3实施例3反应原料以及产物结构及表征汇总
Figure PCTCN2018120966-appb-000025
Figure PCTCN2018120966-appb-000026
Figure PCTCN2018120966-appb-000027
实施例4
中间体H-1的合成
Figure PCTCN2018120966-appb-000028
反应过程：将中间体D-1(16.6g，49.8mmol)、G-1(19.0g，49.8mmol)、碳酸钾(20.6g，149.4mmol)加入到300ml甲苯/乙醇/水(体积比3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基膦) 钯(0.58g，0.5mmol)，再次用氮气置换空气三次，在氮气保护下加热到90℃。
处理过程：TLC监测。待反应结束后，在氮气保护下冷却至室温，使用分液漏斗进行分液，保留有机相。使用硅藻土除去催化剂，用DCM洗硅藻土至无产品。浓缩滤液至少量，硅胶拌样，使用硅胶漏斗进行分离(DCM:PE＝1:10)得到中间体H-1(20.27g，收率78％)。
按照上述方法制备得到表4所示中间体。
表4实施例4反应原料以及产物结构及表征汇总
Figure PCTCN2018120966-appb-000029
Figure PCTCN2018120966-appb-000030
实施例5
中间体I-1的制备
Figure PCTCN2018120966-appb-000031
反应过程：将中间体H-1(20.0g，38.2mmol)加入到200ml DMF溶剂中，加入NBS(13.6g，76.4mmol)，将反应液加热到50℃。
处理过程：TLC监测反应。反应结束后，将反应液浓缩至少许，缓慢滴加到搅拌的石油醚中。待固体析出完全，抽滤，烘干，得到中间体I-1(19.5g，收率85％)。
按照上述方法制备得到表5所示中间体。
表5实施例5反应原料以及产物结构及表征汇总
Figure PCTCN2018120966-appb-000032
Figure PCTCN2018120966-appb-000033
实施例6目标化合物的制备
Figure PCTCN2018120966-appb-000034
反应过程：将中间体I-1(19.5g，32.42mmol)、苯硼酸(5.92g，48.63mmol)、碳酸钾(13.4g，97.26mmol)加入到500ml甲苯/乙醇/水(体积比3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基膦)钯(0.49g，0.32mmol)，再次用氮气置换空气三次，在氮气保护下加热到90℃。
处理过程：TLC监测。待反应结束后，在氮气保护下冷却至室温。使用分液漏斗进行分液，保留有机相。使用硅藻土除去催化剂，用DCM洗硅藻土至无产品。浓缩滤液至少量，硅胶拌样，使用硅胶漏斗进行分离(DCM:PE＝1:5)得到目标化合物K-1(16.87g，收率87％)。
按照上述方法制备得到表6所示中间体。
表6实施例6反应原料以及产物结构及表征汇总
Figure PCTCN2018120966-appb-000035
Figure PCTCN2018120966-appb-000036
Figure PCTCN2018120966-appb-000037
实施例7
有机电致发光器件制备
将费希尔公司涂层厚度为
Figure PCTCN2018120966-appb-000038
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。将已经准备好的ITO透明电极上蒸镀厚度为50nm的4,4',4”-三[2-萘基苯基氨基]三苯基胺(2-TNATA)作为空穴注入层。在形成的空穴注入层上面真空蒸镀厚度为30nm的N'-二(1-萘基)-N,N'-二苯基-(1,1'-联苯)-4,4'-二胺(a-NPD)作为空穴传输层。然后在上述空穴传输层上蒸镀厚度为30nm的蓝色主体材料9,10-二(2-萘基)蒽(AND)和掺杂材料N1,N1,N6,N6-四苯基芘-1,6-二胺(TPPDA)。主体材料和掺杂材料的重量比为95:5。接着在上述发光层上真空蒸镀厚度为10nm的双(2-甲基-8-羟基喹啉-N1,08)-(1,1’-联苯-4-羟基)铝(BAlq)作为空穴阻挡层。在上述空穴阻挡层上真空蒸镀厚度为40nm的如表6所示的本公开制备的化合物中的任意一种，作为电子传输层。在上述电子传输层上真空蒸镀厚度为0.5nm氟化锂(LiF)，作为电子注入层。最后蒸镀厚度为150nm的铝作为阴极，以此完成了有机电致发光器件的制备。
对上述制备的有机电致发光器件加以正向直流偏置电压，利用Photo Research公司的PR-650光度测量设备测定有机电致发光特性，并在5000cd/m 2的基准灰度下利用McScience公司的寿命测定装置测定了T95的寿命。结果见表7。
比较例1
按照实施例7相同的方法制备有机电致发光器件，电子传输层化合物结构如下：
Figure PCTCN2018120966-appb-000039
对制备的有机电致发光器件进行与实施例7相同的检测，结果见表7。
表7实施例7以及比较例1中有机电致发光器件检测结果
Figure PCTCN2018120966-appb-000040
Figure PCTCN2018120966-appb-000041
从上述表7结果中可以看出，使用本公开提供的化合物作为电子传输层所制备的有机电致发光器件，与使用比较例化合物Alq3作为电子传输层所制备的有机电致发光器件相比，驱动电压以及电流密度明显降低，发光效率以及寿命得到显著提高。
以上实施例的说明只是用于帮助理解本公开的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。
工业实用性：
本公开提供了一种蒽类有机发光化合物，具有式I所示结构。本公开提供的新型蒽类有机发光化合物作为有机电致发光器件的电子传输层材料，与其他电子传输层材料相比，发光效率提升明显，寿命改善显著。且所述蒽类有机发光化合物合成路线较短，工艺简单，产率高，原料易得，反应条件温和，成本低，适合工业化生产。

Claims (20)

  1. 一种蒽类有机发光化合物，具有式Ⅰ所示结构：
    Figure PCTCN2018120966-appb-100001
    其中，R 1和R 2独立地选自以下任一基团：
    氢、卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
    取代或非取代的硅基、硼烷基或磷基；
    取代或非取代的C1～C60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
    取代或非取代的C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基；
    且R 1和R 2均不为三嗪基和蒽基；
    R 3选自取代或非取代的C1～C60的烷基、C3～C60的环烷基、C1～C60的杂环基、C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基。
  2. 根据权利要求1所述的蒽类有机发光化合物，其特征在于，具有式Ⅰ-a所示结构：
    Figure PCTCN2018120966-appb-100002
  3. 根据权利要求1所述的蒽类有机发光化合物，其特征在于，所述R 1和R 2独立地选自以下任一基团：
    取代或非取代的C3～C30环烷基、C1～C30杂环基、C6～C30芳基、C7～C30的芳烷基、C6～C30的芳胺基或C6～C30的芳巯基、C2～C30的杂芳基、C10～C30的稠环基；
    R 3选自取代或非取代的C3～C30的环烷基、C1～C30的杂环基、C6～C30芳基、C7～C30的芳烷基、C2～C30的杂芳基、C10～C30的稠环基。
  4. 根据权利要求3所述的蒽类有机发光化合物，其特征在于，所述R 1、R 2和R 3中，取代基选自以下基团：
    卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
    C1～60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
    C6～C60的芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基、C6～C60芳基取代的硅基或C2～C60杂芳基取代的硅基。
  5. 根据权利要求1所述的蒽类有机发光化合物，其特征在于，所述R 1、R 2和R 3独立地选自以下任一基团：
    取代或非取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基；
    或者2～6个任意以上基团形成的稠环基团；
    或者2～6个任意以上基团通过单键、N、O、B、Si、P、P＝O、S或S＝O连接形成的基团；
    上述基团的任意一个或多个C原子可被O、S、N或Si取代；
    上述基团或取代基团的H原子可被氘代；
    上述取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的取代基团独立地选自：
    卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
    C1～60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
    C6～C60的芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基、C6～C60芳基取代的硅基或C2～C60杂芳基取代的硅基。
  6. 根据权利要求5所述的蒽类有机发光化合物，其特征在于，所述R 1、R 2和R 3独立地选自以下任一基团，或者2个以上任意基团由单键连接形成的基团：
    Figure PCTCN2018120966-appb-100003
    其中，X和Y独立地选自氢原子、卤素原子、氰基、硝基、羟基、氨基、取代或未取代的C1～C30的烷基、C3～C30的环烷基、C1～C30的烷氧基、C2～C30的烯基、C7～C30的烷芳基、C7～C30的烷芳氧基、C6～C30的芳基、C6～C30的芳氧基、C2～C30的杂环基、C5～C30的杂芳基或C6～C30的芳香族胺；
    Q为C或N；
    P为C、N、O或S；
    Z为O或S。
  7. 根据权利要求6所述的蒽类有机发光化合物，其特征在于，具有以下结构：
    Figure PCTCN2018120966-appb-100004
    Figure PCTCN2018120966-appb-100005
    Figure PCTCN2018120966-appb-100006
    Figure PCTCN2018120966-appb-100007
    Figure PCTCN2018120966-appb-100008
    Figure PCTCN2018120966-appb-100009
  8. 一种蒽类有机发光化合物的制备方法，包括以下步骤：
    式Ⅱ所示化合物和式Ⅲ所示化合物进行缩合反应，得到式Ⅳ所示化合物；
    式Ⅳ所示化合物经溴化，得到式Ⅴ所示化合物；
    式Ⅴ所示化合物和R 1-B(OH) 2反应，得到式Ⅰ所示化合物；
    Figure PCTCN2018120966-appb-100010
    其中，R 1和R 2独立地选自以下任一基团：
    氢、卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
    取代或非取代的硅基、硼烷基或磷基；
    取代或非取代的C1～C60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
    取代或非取代的C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基；
    且R 1和R 2均不为三嗪基和蒽基；
    R 3选自取代或非取代的C1～C60的烷基、C3～C60的环烷基、C1～C60的杂环基、C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基。
  9. 根据权利要求8所述的蒽类有机发光化合物的制备方法，其特征在于，所述式Ⅱ所示化合物和式Ⅲ所示化合物的缩合反应以及所述式Ⅴ所示化合物和R 1-B(OH) 2的反应均由钯催化剂催化。
  10. 根据权利要求9所述的蒽类有机发光化合物的制备方法，其特征在于，所述钯催化剂为四(三苯基膦)钯。
  11. 一种有机电致发光器件，包括权利要求1～7任意一项所述的蒽类有机发光化合物或权利要求8～10任意一项所述的制备方法制备的蒽类有机发光化合物。
  12. 一种有机电致发光器件，其特征在于，所述有机电致发光器件包括第一电极、第二电极和设置于所述第一电极与第二电极之间的有机物层。
  13. 根据权利要求12所述的有机电致发光器件，其特征在于，所述有机物层包括权利要求1～7任意一项所述的蒽类有机发光化合物或权利要求8～10任意一项所述的制备方法制备的蒽类有机发光化合物。
  14. 根据权利要求12或13所述的有机电致发光器件，其特征在于，所述有机物层进一步包括空穴注入层、空穴传输层、同时具备空穴注入和空穴传输技能层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层以及同时具备电子传输和电子注入技能层中的一层或多层。
  15. 根据权利要求12～14任意一项所述的有机电致发光器件，其特征在于，所述有机物层包括发光层。
  16. 根据权利要求12～15任意一项所述的有机电致发光器件，其特征在于，所述有机 物层包括电子传输层，并且所述电子传输层包括权利要求1～7任意一项所述的蒽类有机发光化合物或权利要求8～10任意一项所述的制备方法制备的蒽类有机发光化合物。
  17. 根据权利要求12～16任意一项所述的有机电致发光器件，其特征在于，所述有机物层包括电子传输层，并且所述电子传输层包括金属化合物。
  18. 根据权利要求12～17任意一项所述的有机电致发光器件，其特征在于，所述有机物层包括发光层与电子传输层，并且所述发光层与电子传输层分别包括结构相同或不相同的权利要求1所述式I所示的蒽类有机发光化合物。
  19. 一种有机光电材料，其特征在于，包括权利要求1～7任意一项所述的蒽类有机发光化合物或权利要求8～10任意一项所述的制备方法制备的蒽类有机发光化合物；所述有机光电材料包括有机太阳电池、电子纸、有机感光体或有机晶体管。
  20. 一种有机光电材料在制备有机电致发光器件、有机太阳电池、电子纸、有机感光体或有机晶体管中的应用，其特征在于，所述有机光电材料包括权利要求1～7任意一项所述的蒽类有机发光化合物或权利要求8～10任意一项所述的制备方法制备的蒽类有机发光化合物。
PCT/CN2018/120966 2018-06-28 2018-12-13 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件 WO2020000921A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810691248.5 2018-06-28
CN201810691248.5A CN108794404B (zh) 2018-06-28 2018-06-28 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件

Publications (1)

Publication Number Publication Date
WO2020000921A1 true WO2020000921A1 (zh) 2020-01-02

Family

ID=64072417

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/120966 WO2020000921A1 (zh) 2018-06-28 2018-12-13 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件

Country Status (2)

Country Link
CN (1) CN108794404B (zh)
WO (1) WO2020000921A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108794404B (zh) * 2018-06-28 2020-08-21 吉林奥来德光电材料股份有限公司 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件
CN110818687B (zh) * 2018-08-08 2022-05-03 北京鼎材科技有限公司 化合物及有机电致发光器件
CN109879812A (zh) * 2019-04-22 2019-06-14 吉林奥来德光电材料股份有限公司 蒽类有机发光化合物及其制备方法和应用
CN109879811A (zh) * 2019-04-22 2019-06-14 吉林奥来德光电材料股份有限公司 有机发光材料及制备方法和应用
CN115286581B (zh) * 2022-08-02 2024-03-22 吉林大学 具有高固态发光效率的纯有机单分子白光材料及其在制备有机电致白光器件中的应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1462303A (zh) * 2001-04-27 2003-12-17 Lg化学株式会社 双螺环有机化合物和电场致发光器件
CN101560136A (zh) * 2008-04-02 2009-10-21 葛来西雅帝史派有限公司 新颖的有机电致发光化合物和使用该化合物的有机电致发光器件
CN103865525A (zh) * 2014-04-01 2014-06-18 上海道亦化工科技有限公司 一种有机电致发光化合物
CN106910834A (zh) * 2015-12-22 2017-06-30 三星显示有限公司 有机发光器件
CN107602467A (zh) * 2017-09-18 2018-01-19 长春海谱润斯科技有限公司 一种含蒽类化合物及其合成方法和有机电致发光器件
CN108794404A (zh) * 2018-06-28 2018-11-13 吉林奥来德光电材料股份有限公司 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1462303A (zh) * 2001-04-27 2003-12-17 Lg化学株式会社 双螺环有机化合物和电场致发光器件
CN101560136A (zh) * 2008-04-02 2009-10-21 葛来西雅帝史派有限公司 新颖的有机电致发光化合物和使用该化合物的有机电致发光器件
CN103865525A (zh) * 2014-04-01 2014-06-18 上海道亦化工科技有限公司 一种有机电致发光化合物
CN106910834A (zh) * 2015-12-22 2017-06-30 三星显示有限公司 有机发光器件
CN107602467A (zh) * 2017-09-18 2018-01-19 长春海谱润斯科技有限公司 一种含蒽类化合物及其合成方法和有机电致发光器件
CN108794404A (zh) * 2018-06-28 2018-11-13 吉林奥来德光电材料股份有限公司 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件

Also Published As

Publication number Publication date
CN108794404A (zh) 2018-11-13
CN108794404B (zh) 2020-08-21

Similar Documents

Publication Publication Date Title
KR100940938B1 (ko) 신규한 유기 발광 화합물 및 이를 발광재료로서 채용하고있는 유기 전기 발광 소자
KR101063940B1 (ko) 신규한 유기 화합물 및 이를 이용한 유기 발광 소자
WO2020000921A1 (zh) 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件
WO2017043757A1 (ko) 유기 화합물, 유기 광전자 소자 및 표시 장치
WO2014104515A1 (ko) 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
KR20160039492A (ko) 유기 광전자 소자용 화합물 및 이를 포함하는 유기 광전자 소자
WO2021008374A1 (zh) 一种新型化合物及其应用及采用该化合物的有机电致发光器件
WO2023284103A1 (zh) 一种有机化合物及其应用
CN113004290A (zh) 一种有机化合物、有机电致发光材料及其应用
CN112778253B (zh) 有机化合物及含有其的有机电致发光器件
WO2020000920A1 (zh) 一种有机发光化合物及其制备方法和有机电致发光器件
JP2020535185A (ja) ヘテロ環化合物およびこれを含む有機発光素子
KR20140087987A (ko) 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치
KR20130121597A (ko) 트리페닐아민을 사용한 정공 수송 물질 및 이를 포함한 유기 전계 발광 소자
WO2023125276A1 (zh) 一种有机化合物及其应用
WO2021121230A1 (zh) 一种化合物及其应用、包含其的有机电致发光器件
CN111747932B (zh) 一种化合物及其应用、有机电致发光器件
TWI471308B (zh) 有機化合物及包含其之有機電激發光裝置
WO2023231531A1 (zh) 含氮化合物、有机电致发光器件和电子装置
CN112979535A (zh) 一种化合物及其应用
CN108264486B (zh) 一种新颖的咪唑类化合物及其制备和电致发光器件
CN112745301B (zh) 有机化合物及含有其的有机电致发光器件
CN115160342A (zh) 一种化合物及其应用、包含其的有机电致发光器件
CN114685411A (zh) 有机化合物及其应用、有机电致发光器件
KR102146791B1 (ko) 유기 광전자 소자용 화합물, 유기 광전자 소자 및 표시 장치

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18924671

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18924671

Country of ref document: EP

Kind code of ref document: A1