CN113861143A - 一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件 - Google Patents

一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件 Download PDF

Info

Publication number
CN113861143A
CN113861143A CN202111187348.2A CN202111187348A CN113861143A CN 113861143 A CN113861143 A CN 113861143A CN 202111187348 A CN202111187348 A CN 202111187348A CN 113861143 A CN113861143 A CN 113861143A
Authority
CN
China
Prior art keywords
solvent
delayed fluorescence
blue light
deep blue
thermally activated
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
CN202111187348.2A
Other languages
English (en)
Other versions
CN113861143B (zh
Inventor
孟鸿
张鑫康
王胧佩
邹东文
贺耀武
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.)
Peking University Shenzhen Graduate School
Original Assignee
Peking University Shenzhen Graduate School
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 Peking University Shenzhen Graduate School filed Critical Peking University Shenzhen Graduate School
Priority to CN202111187348.2A priority Critical patent/CN113861143B/zh
Publication of CN113861143A publication Critical patent/CN113861143A/zh
Application granted granted Critical
Publication of CN113861143B publication Critical patent/CN113861143B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D345/00—Heterocyclic compounds containing rings having selenium or tellurium atoms as the only ring hetero atoms
    • 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
    • C07D409/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D413/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D417/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D421/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing two hetero rings
    • C07D421/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D421/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing three or more hetero 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring 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 Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
    • C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
    • C07F9/655354—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • 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
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds
    • 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
    • C09K2211/1018—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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms 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
    • C09K2211/1059—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
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—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

Landscapes

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

Abstract

本发明公开一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件，所述热激活延迟荧光深蓝光材料具有如下结构：D—A或D—A—D，D为基于五元杂环的电子给体单元，基于五元杂环的电子给体单元的结构式为：
Figure DDA0003299801530000011
或
Figure DDA0003299801530000012
其中，X、Y各自独立地选自氧、硫、硒、碲或氮烷基，R1‑R4各自独立地选自氢、氘、氰基或烷基链；A为电子受体单元；“
Figure DDA0003299801530000013
”表示连接位点。基于五元杂环的电子给体单元具有刚性结构，使得热激活延迟荧光材料具有较高的荧光效率。该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料且具有寿命长和发光率高的优点。

Description

一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发 光器件
技术领域
本发明涉及有机电致发光材料领域，尤其涉及一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件。
背景技术
有机发光二极管因具有柔性显示、色域广、视角宽等诸多优点，在手机、平板电脑、电视和穿戴设备等领域有着广泛的应用，深蓝光材料是当前有机发光二极管产业界的核心材料。当前商业化产品中以传统荧光材料为主，但其发光效率低，而使用贵金属的蓝光磷光材料配位键较弱，发光稳定性差。
热激活延迟荧光蓝光材料效率较高，是目前最有希望替代传统荧光材料的选择。然而，当前普遍采用的热激活延迟荧光蓝光材料多以咔唑、苯胺等含氮富电子基团作为电子给体，但是在高亮度下其连接键易解离，咔唑、苯胺等基团的引入不利于器件寿命的提升。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件，旨在解决现有热激活延迟荧光蓝光材料制备的有机电致发光器件寿命较低的问题。
本发明的技术方案如下：
本发明的第一方面，提供一种热激活延迟荧光深蓝光材料，其中，所述热激活延迟荧光深蓝光材料具有如下结构：
D—A或D—A—D，
D为基于五元杂环的电子给体单元，所述基于五元杂环的电子给体单元的结构式为：
Figure BDA0003299801510000011
其中，X、Y各自独立地选自氧、硫、硒、碲或氮烷基，R1-R4各自独立地选自氢、氘、氰基或烷基链；A为电子受体单元；
Figure BDA0003299801510000012
表示连接位点。
可选地，所述电子受体单元具有以下结构中的一种：
Figure BDA0003299801510000021
其中
Figure BDA0003299801510000022
表示连接位点。
可选地，所述热激活延迟荧光深蓝光材料具有以下结构中的一种：
Figure BDA0003299801510000023
Figure BDA0003299801510000031
Figure BDA0003299801510000041
Figure BDA0003299801510000051
本发明的第二方面，提供一种如上所述的热激活延迟荧光深蓝光材料的制备方法，其中，当D选自
Figure BDA0003299801510000052
R1-R4选自氢时，包括步骤：
将
Figure BDA0003299801510000053
与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到
Figure BDA0003299801510000054
将
Figure BDA0003299801510000055
与
Figure BDA0003299801510000056
溶解在第二溶剂中，反应后得到
Figure BDA0003299801510000057
可选地，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将
Figure BDA0003299801510000058
与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到
Figure BDA0003299801510000059
在无水无氧条件下，将
Figure BDA00032998015100000510
与
Figure BDA00032998015100000511
四三苯基膦钯、碳酸钾溶解在第二溶剂中，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA0003299801510000061
本发明的第三方面，提供又一种如上所述的热激活延迟荧光深蓝光材料的制备方法，其中，当D选自
Figure BDA0003299801510000062
R1-R4选自氢时，包括步骤：
将
Figure BDA0003299801510000063
与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到
Figure BDA0003299801510000064
将
Figure BDA0003299801510000065
与
Figure BDA0003299801510000066
溶解在第三溶剂中，反应后得到
Figure BDA0003299801510000067
将
Figure BDA0003299801510000068
与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，反应后得到
Figure BDA0003299801510000069
将
Figure BDA00032998015100000610
与N-溴代琥珀酰亚胺溶解在第四溶剂中，反应后得到
Figure BDA00032998015100000611
将
Figure BDA00032998015100000612
与
Figure BDA00032998015100000613
溶解在第二溶剂中，反应后得到
Figure BDA00032998015100000614
可选地，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将
Figure BDA00032998015100000615
与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到
Figure BDA00032998015100000616
在无水无氧条件下，将
Figure BDA00032998015100000617
与
Figure BDA00032998015100000618
溶解在第三溶剂中，60-80℃下反应16-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱分离得到
Figure BDA0003299801510000071
在无氧条件下，将
Figure BDA0003299801510000072
与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，搅拌回流12-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA0003299801510000073
在无水无氧条件下，将
Figure BDA0003299801510000074
与N-溴代琥珀酰亚胺溶解在第四溶剂中，在80-100℃下反应12-24小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA0003299801510000075
在无水无氧条件下，将
Figure BDA0003299801510000076
与
Figure BDA0003299801510000077
四三苯基膦钯、碳酸钾溶解在第二溶剂，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA0003299801510000078
可选地，所述第一溶剂为二氯甲烷；和/或，
所述第二溶剂为分子筛脱水的甲苯；和/或，
所述第三溶剂为N,N-二甲基甲酰胺；和/或，
所述第四溶剂为聚碳酸酯。
本发明的第四方面，提供一种有机电致发光器件，包括发光层，其中，所述发光层的材料包括如上所述的热激活延迟荧光深蓝光材料。
有益效果：本发明提供了一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件。所述基于五元杂环的电子给体单元具有刚性结构，可将其作为热激活延迟荧光材料的电子给体，由于前线分子轨道在电子给体和电子受体上的充分分离，能够使得热激活延迟荧光材料利用暗激子，从而具有较高荧光效率。同时该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料。将所述热激活延迟荧光深蓝光材料用于制备有机电致发光器件时，由于材料本身发光效率高，而且基团之间均为稳定的C-C键连接，可以使得有机电致发光器件具有较长的寿命和较高的发光效率。
附图说明
图1为本发明实施例4中有机电致发光器件的结构示意图。
图2为本发明实施例3中化合物99的光致发光荧光光谱图。
具体实施方式
本发明提供一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供一种热激活延迟荧光深蓝光材料，其中，所述热激活延迟荧光深蓝光材料具有如下结构：
D—A或D—A—D，
D为基于五元杂环的电子给体单元，所述基于五元杂环的电子给体单元的结构式为：
Figure BDA0003299801510000081
其中，X、Y各自独立地选自氧、硫、硒、碲或氮烷基，R1-R4各自独立地选自氢、氘、氰基或烷基链；A为电子受体单元；
Figure BDA0003299801510000082
表示连接位点。
本实施例中，X、Y可以相同，也可以不同，他们各自独立地选自氧、硫、硒、碲或氮烷基。R1-R4可以相同，也可以不同，他们各自独立地选自氢、氘、氰基或烷基链。D1中的连接位点可在X的邻位，也可在X的间位；D2中的连接位点可以在R1或R2的邻位，也可以在R1或R2的间位，可以在R3或R4的邻位，也可以在R3或R4的间位。
上述基于五元杂环的电子给体单元具有刚性结构，可将其作为热激活延迟荧光材料的电子给体，由于前线分子轨道在电子给体和电子受体上的充分分离，将上述基于五元杂环的电子给体单元作为热激活延迟荧光材料的电子给体时，能够使得热激活延迟荧光材料利用暗激子，从而具有较高的荧光效率。同时该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料。
将所述热激活延迟荧光深蓝光材料用于制备有机电致发光器件时，由于材料本身发光效率高，而且基团之间均为稳定的C-C键连接，可以使得有机电致发光器件具有较长的寿命和较高的发光效率。
在一种实施方式中，所述电子受体单元具有以下结构中的一种：
Figure BDA0003299801510000091
其中
Figure BDA0003299801510000092
表示连接位点。
上述结构的电子受体单元可以使得热激活延迟荧光深蓝光材料具有更深的最高电子占据轨道，从而实现深蓝光发射。
在一种实施方式中，所述热激活延迟荧光深蓝光材料具有以下结构中的一种：
Figure BDA0003299801510000093
Figure BDA0003299801510000101
Figure BDA0003299801510000111
Figure BDA0003299801510000121
本发明实施例还提供一种如上所述的热激活延迟荧光深蓝光材料的制备方法，以所述热激活延迟荧光深蓝光材料具有D-A结构为例，其中，当D选自
Figure BDA0003299801510000122
R1-R4选自氢时，包括步骤：
将
Figure BDA0003299801510000123
与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到
Figure BDA0003299801510000124
将
Figure BDA0003299801510000125
与
Figure BDA0003299801510000126
溶解在第二溶剂中，反应后得到
Figure BDA0003299801510000127
本发明实施例提供的制备方法，以
Figure BDA0003299801510000128
为反应物，依次通过亲电取代反应、Suzuki反应，引入电子受体单元，制备得到
Figure BDA0003299801510000129
该制备方法操作相对简单，制备得到的
Figure BDA00032998015100001210
产率高。
在一种实施方式中，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将
Figure BDA0003299801510000131
与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到
Figure BDA0003299801510000132
在无水无氧条件下，将
Figure BDA0003299801510000133
与
Figure BDA0003299801510000134
四三苯基膦钯、碳酸钾溶解在第二溶剂中，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA0003299801510000135
具体地，
Figure BDA0003299801510000136
的合成路线为：
Figure BDA0003299801510000137
本发明实施例提供了另一种如上所述的热激活延迟荧光深蓝光材料的制备方法，以所述热激活延迟荧光深蓝光材料具有D-A结构为例，其中，当D选自
Figure BDA0003299801510000138
R1-R4选自氢时，包括步骤：
将
Figure BDA0003299801510000139
与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到
Figure BDA00032998015100001310
将
Figure BDA00032998015100001311
与
Figure BDA00032998015100001312
溶解在第三溶剂中，反应后得到
Figure BDA00032998015100001313
将
Figure BDA00032998015100001314
与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，反应后得到
Figure BDA00032998015100001315
将
Figure BDA0003299801510000141
与N-溴代琥珀酰亚胺溶解在第四溶剂中，反应后得到
Figure BDA0003299801510000142
将
Figure BDA0003299801510000143
与
Figure BDA0003299801510000144
溶解在第二溶剂中，反应后得到
Figure BDA0003299801510000145
本发明实施例提供的制备方法，以
Figure BDA0003299801510000146
为反应物，依次通过亲电取代反应、芳环亲电取代反应、环化反应、卤代反应、Suzuki反应，引入电子受体单元，制备得到
Figure BDA0003299801510000147
该制备方法操作相对简单，制备得到的
Figure BDA0003299801510000148
产率高。
在一种实施方式中，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将
Figure BDA0003299801510000149
与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到
Figure BDA00032998015100001410
在无水无氧条件下，将
Figure BDA00032998015100001411
与
Figure BDA00032998015100001412
溶解在第三溶剂中，60-80℃下反应16-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱分离得到
Figure BDA00032998015100001413
在无氧条件下，将
Figure BDA00032998015100001414
与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，搅拌回流12-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA00032998015100001415
在无水无氧条件下，将
Figure BDA00032998015100001416
与N-溴代琥珀酰亚胺溶解在第四溶剂中，在80-100℃下反应12-24小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA0003299801510000151
在无水无氧条件下，将
Figure BDA0003299801510000152
与
Figure BDA0003299801510000153
四三苯基膦钯、碳酸钾溶解在第二溶剂，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到
Figure BDA0003299801510000154
具体地，
Figure BDA0003299801510000155
的合成路线为：
Figure BDA0003299801510000156
在一种实施方式中，所述第一溶剂为二氯甲烷，但不限于此。
在一种实施方式中，所述第二溶剂为分子筛脱水的甲苯，但不限于此。
在一种实施方式中，所述第三溶剂为N,N-二甲基甲酰胺，但不限于此。
在一种实施方式中，所述第四溶剂为聚碳酸酯，但不限于此。
本发明实施例还提供一种有机电致发光器件，包括发光层，其中，所述发光层的材料包括本发明实施例如上所述的热激活延迟荧光深蓝光材料。
本实施例中，有机电致发光器件寿命长、发光效率高。
下面通过具体的实施例对本发明作进一步地说明。
需要说明的是，以下实施例中所用试剂或仪器未注明生产厂商的，均为可通过市购购买获得的常规产品。实施例中未提及其合成方法的化合物均为可通过商业途径获得的原料产品。实施例中所用溶剂和试剂均可从国内化工市场购买，例如购买自国药集团试剂公司，安耐吉公司，阿拉丁公司，上海毕得医药公司等，另外，本领域技术人员也可以通过公知方法进行合成。实施例中未注明具体实验步骤或反应条件的，按照本领域内熟知的常规实验步骤或反应条件即可进行。
实施例1
本实施例提供一种热激活延迟荧光深蓝光材料，记作化合物4，化合物4的合成路线如下所示：
Figure BDA0003299801510000161
化合物4的合成方法具体包括以下步骤：
中间体1的合成：在无水无氧条件下，将原料1(13.4g，100mmol)、N-溴代琥珀酰亚胺(21.4g，120mmol)和二氯甲烷(200mL)放入圆底烧瓶中，常温下反应12小时，加入饱和硫代硫酸钠溶液(50mL)淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤。使用无水硫酸钠干燥后，粗产物以硅胶柱层析(石油醚/乙酸乙酯为3/1(体积比))纯化，得到中间体1(20.2g，产率95％)。
化合物4的合成：取双颈圆底烧瓶(500mL)，上接球形冷凝管，干燥后充入氮气，分别加入中间体1(10.7g，50mmol)，原料2(16.9g，55mmol)，四三苯基膦钯(458mg，0.5mmol)，碳酸钾水溶液(2mol/L，75mL)，甲苯(200mL)。加热回流24小时，冷却至室温，将溶液倒入水中，使用二氯甲烷萃取，水相用乙酸乙酯萃取三次，合并有机相，使用无水硫酸钠干燥后，粗产物以硅胶柱层析(石油醚/乙酸乙酯为4/1(体积比))纯化，得到化合物4(10.9g，产率70％)。高分辨质谱：314.0612(理论值314.0765)。
实施例2
本实施例提供一种热激活延迟荧光深蓝光材料，记作化合物70，化合物70的合成路线如下所示：
Figure BDA0003299801510000162
化合物70的合成方法具体包括以下步骤：
中间体2的合成：同实施例1中中间体1的合成，区别仅在于：使用原料3(11.8g，100mmol)，得到中间体2(17.3g，产率88％)。
化合物70的合成：同实施例1中化合物4的合成，区别仅在于：使用中间体2(9.8g，50mmol)，原料4(21.0g，55mmol)，得到化合物70(5.9g，产率65％)。高分辨质谱：362.0920(理论值362.1055)。
实施例3
本实施例提供一种热激活延迟荧光深蓝光材料，记作化合物99，化合物99的合成路线如下所示：
Figure BDA0003299801510000171
化合物99的合成方法具体包括以下步骤：
中间体1的合成：同实施例1中中间体1的合成。
中间体3的合成：在无水无氧条件下，将中间体1(4.26g，20mmol)、苯硫酚(42.42g，22mmol)、碳酸钾(5.52g)和干燥的N,N-二甲基甲酰胺(100mL)放入圆底烧瓶中，60-80℃下反应20小时，将溶液倒入水中，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤。使用无水硫酸钠干燥后，粗产物以硅胶柱层析(石油醚/乙酸乙酯为5/1(体积比))纯化，得到中间体3(3.98g，产率82％)。
中间体4的合成：在无氧条件下，将中间体3(2.42g，10mmol)与催化量Pd(OPiv)2和Ag(OPiv)溶于甲苯(50mL)中，搅拌回流16小时，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱(石油醚/乙酸乙酯为3/1(体积比)分离，得到中间体4(2.04g，产率85％)。
中间体5的合成：在无水无氧条件下，将中间体4(1.20g，5mmol)与N-溴代琥珀酰亚胺(1.07g，6mmol)溶于聚碳酸酯(50mL)中，在80℃下反应20小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱(石油醚/乙酸乙酯为5/1(体积比)分离，得到中间体5(1.49g，产率93％)。
化合物99的合成：同实施例1中化合物4的合成，区别仅在于：使用中间体5(0.32g，1.0mmol)，原料6(0.98g，2.2mmol)，得到化合物99(0.47g，产率71％)。高分辨质谱：667.9557(理论值667.9638)。
实施例4
本实施例提供了一种有机电致发光器件，如图1所示，包括从上至下依次层叠设置的金属阴极1、电子注入层2、电子传输层3、发光层4、空穴传输层5、空穴注入层6、阳极7以及玻璃基板8。
其中，金属阴极1选用铝；电子注入层2选用氟化锂；电子传输层3选用化合物LET003，其结构式为
Figure BDA0003299801510000181
发光层4由主体材料和客体材料共掺杂形成，其中主体材料选用化合物mCBP，其结构式为
Figure BDA0003299801510000182
客体材料选用实施例3中制备得到的化合物99，主体材料与客体材料掺杂的质量比为85：15；空穴传输层5选用化合物NPB，其结构式为
Figure BDA0003299801510000183
空穴注入层6选用化合物HATCN，其结构式为
Figure BDA0003299801510000184
阳极7选用氧化铟锡。
实施例5
本实施例提供了一种有机电致发光器件，与实施例4中提供的有机电致发光器件的区别仅在于：发光层4的客体材料选用实施例1中制备得到的化合物4。
实施例6
本实施例提供了一种有机电致发光器件，与实施例4中提供的有机电致发光器件的区别仅在于：发光层4的客体材料选用实施例2中制备的化合物70。
对比例1
本对比例提供了一种有机电致发光器件，与实施例4中提供的有机电致发光器件的区别仅在于：发光层4的客体材料选用商业化材料5TCzBN(2,3,4,5,6-五(3,6-二叔丁基-9H-咔唑-9-基)苯甲腈)。
测试
(1)对实施例3制备得到的化合物99进行光致发光测试，其光致发光荧光光谱如图2所示，由此结果可知，化合物99可发深蓝光。
(2)对实施例4和对比例1中的有机电致发光器件进行发光效率测试，结果如表1所示，可以看出，对比采用传统咔唑5TCzBN作为电子给体的发光材料，采用新型五元杂环作为电子给体的化合物99显示出更高的电致发光亮度和更高的量子效率，同时器件寿命是对比器件的两倍以上，因此该新型五元杂环作为电子给体的发光材料更具商业化潜力。
表1发光效率测试结果
Figure BDA0003299801510000191
综上所述，本发明提供一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件。所述基于五元杂环的电子给体单元具有刚性结构，可将其作为热激活延迟荧光材料的电子给体，由于前线分子轨道在电子给体和受体上的充分分离，能够使得热激活延迟荧光材料利用暗激子，从而具有较高荧光效率率。同时该系列五元杂环在基本不影响分子最低未占据轨道的情况下有效地降低分子最高占据轨道，从而增大带隙，使分子发光光谱蓝移至深蓝光区，从而可得到热激活延迟荧光深蓝光材料。将所述热激活延迟荧光深蓝光材料用于制备有机电致发光器件时，由于材料本身发光效率高，而且基团之间均为稳定的C-C键连接，可以使得有机电致发光器件具有较长的寿命和较高的发光效率。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (9)

1.一种热激活延迟荧光深蓝光材料，其特征在于，所述热激活延迟荧光深蓝光材料具有如下结构：
D—A或D—A—D，
D为基于五元杂环的电子给体单元，所述基于五元杂环的电子给体单元的结构式为：
Figure FDA0003299801500000011
其中，X、Y各自独立地选自氧、硫、硒、碲或氮烷基，R1-R4各自独立地选自氢、氘、氰基或烷基链；A为电子受体单元；
Figure FDA0003299801500000012
表示连接位点。
2.根据权利要求1所述的热激活延迟荧光深蓝光材料，其特征在于，所述电子受体单元具有以下结构中的一种：
Figure FDA0003299801500000013
其中
Figure FDA0003299801500000014
表示连接位点。
3.根据权利要求1所述的热激活延迟荧光深蓝光材料，其特征在于，所述热激活延迟荧光深蓝光材料具有以下结构中的一种：
Figure FDA0003299801500000021
Figure FDA0003299801500000031
Figure FDA0003299801500000041
4.一种如权利要求1所述的热激活延迟荧光深蓝光材料的制备方法，其特征在于，当D选自
Figure FDA0003299801500000051
R1-R4选自氢时，包括步骤：
将
Figure FDA0003299801500000052
与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到
Figure FDA0003299801500000053
将
Figure FDA0003299801500000054
与
Figure FDA0003299801500000055
溶解在第二溶剂中，反应后得到
Figure FDA0003299801500000056
5.根据权利要求4所述的热激活延迟荧光深蓝光材料的制备方法，其特征在于，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将
Figure FDA0003299801500000057
与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到
Figure FDA0003299801500000058
在无水无氧条件下，将
Figure FDA0003299801500000059
与
Figure FDA00032998015000000510
四三苯基膦钯、碳酸钾溶解在第二溶剂中，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到
Figure FDA00032998015000000511
6.一种如权利要求1所述的热激活延迟荧光深蓝光材料的制备方法，其特征在于，当D选自
Figure FDA00032998015000000512
R1-R4选自氢时，包括步骤：
将
Figure FDA0003299801500000061
与N-溴代琥珀酰亚胺溶解在第一溶剂中，反应后得到
Figure FDA0003299801500000062
将
Figure FDA0003299801500000063
与
Figure FDA0003299801500000064
溶解在第三溶剂中，反应后得到
Figure FDA0003299801500000065
将
Figure FDA0003299801500000066
与Pd(OPiv)2，Ag(OPiv)溶解在第二溶剂中，反应后得到
Figure FDA0003299801500000067
将
Figure FDA0003299801500000068
与N-溴代琥珀酰亚胺溶解在第四溶剂中，反应后得到
Figure FDA0003299801500000069
将
Figure FDA00032998015000000610
与
Figure FDA00032998015000000611
溶解在第二溶剂中，反应后得到
Figure FDA00032998015000000612
7.根据权利要求6所述的热激活延迟荧光深蓝光材料的制备方法，其特征在于，所述热激活延迟荧光深蓝光材料的制备方法具体包括步骤：
在无水无氧条件下，将
Figure FDA00032998015000000613
与N-溴代琥珀酰亚胺溶解在第一溶剂中，常温下反应12小时后加入饱和硫代硫酸钠溶液淬灭，分液后有机相依次用饱和碳酸钠溶液、去离子水洗涤，然后用无水硫酸钠干燥后，通过色谱柱分离得到
Figure FDA00032998015000000614
在无水无氧条件下，将
Figure FDA00032998015000000615
与
Figure FDA00032998015000000616
溶解在第三溶剂中，60-80℃下反应16-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥后，通过色谱柱分离得到
Figure FDA00032998015000000617
在无氧条件下，将
Figure FDA00032998015000000618
与Pd(OPiv)2、Ag(OPiv)溶解在第二溶剂中，搅拌回流12-24小时后，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
Figure FDA00032998015000000619
在无水无氧条件下，将
Figure FDA0003299801500000071
与N-溴代琥珀酰亚胺溶解在第四溶剂中，在80-100℃下反应12-24小时后冷却至室温，将溶液倒入水中，用二氯甲烷提取、无水硫酸钠干燥，通过色谱柱分离得到
Figure FDA0003299801500000072
在无水无氧条件下，将
Figure FDA0003299801500000073
与
Figure FDA0003299801500000074
四三苯基膦钯、碳酸钾溶解在第二溶剂中，90-110℃下反应12-24小时后，加入去离子水，用第一溶剂萃取，用无水硫酸钠干燥，通过色谱柱分离得到
Figure FDA0003299801500000075
8.根据权利要求4-7任一项所述的热激活延迟荧光深蓝光材料的制备方法，其特征在于，
所述第一溶剂为二氯甲烷；和/或，
所述第二溶剂为分子筛脱水的甲苯；和/或，
所述第三溶剂为N,N-二甲基甲酰胺；和/或，
所述第四溶剂为聚碳酸酯。
9.一种有机电致发光器件，包括发光层，其特征在于，所述发光层的材料包括权利要求1-3任一项所述的热激活延迟荧光深蓝光材料。
CN202111187348.2A 2021-10-12 2021-10-12 一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件 Active CN113861143B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111187348.2A CN113861143B (zh) 2021-10-12 2021-10-12 一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111187348.2A CN113861143B (zh) 2021-10-12 2021-10-12 一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件

Publications (2)

Publication Number Publication Date
CN113861143A true CN113861143A (zh) 2021-12-31
CN113861143B CN113861143B (zh) 2023-12-12

Family

ID=78999083

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111187348.2A Active CN113861143B (zh) 2021-10-12 2021-10-12 一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件

Country Status (1)

Country Link
CN (1) CN113861143B (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022262310A1 (zh) * 2021-06-17 2022-12-22 广东阿格蕾雅光电材料有限公司 Btbf芳胺衍生物的合成方法
CN115960064A (zh) * 2023-01-15 2023-04-14 西安交通大学 一种荧光发射材料及有机电致发光器件
WO2024119296A1 (en) * 2022-12-05 2024-06-13 Boe Technology Group Co., Ltd. Emissive material, light-emitting diode, and display apparatus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007217397A (ja) * 2005-08-01 2007-08-30 Mitsubishi Chemicals Corp 遷移金属錯体の製造方法
CN103140493A (zh) * 2010-07-21 2013-06-05 赫劳斯贵金属有限两和公司 基于取代的[1]苯并噻吩并[3,2-b][1]苯并噻吩的半导体
KR20150004493A (ko) * 2013-07-02 2015-01-13 주식회사 두산 유기 화합물 및 이를 포함하는 유기 전계 발광 소자
CN110734453A (zh) * 2018-07-18 2020-01-31 北京大学深圳研究生院 一种胺类衍生物及其制备方法、有机发光二极管
CN113121560A (zh) * 2021-03-29 2021-07-16 北京大学深圳研究生院 一种苯并噻吩并苯并五元杂环材料及其制备方法与应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007217397A (ja) * 2005-08-01 2007-08-30 Mitsubishi Chemicals Corp 遷移金属錯体の製造方法
CN103140493A (zh) * 2010-07-21 2013-06-05 赫劳斯贵金属有限两和公司 基于取代的[1]苯并噻吩并[3,2-b][1]苯并噻吩的半导体
KR20150004493A (ko) * 2013-07-02 2015-01-13 주식회사 두산 유기 화합물 및 이를 포함하는 유기 전계 발광 소자
CN110734453A (zh) * 2018-07-18 2020-01-31 北京大学深圳研究生院 一种胺类衍生物及其制备方法、有机发光二极管
CN113121560A (zh) * 2021-03-29 2021-07-16 北京大学深圳研究生院 一种苯并噻吩并苯并五元杂环材料及其制备方法与应用

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
FANG-FANG ZHUO ET AL.: "TMEDA-Assisted Effective Direct Ortho Arylation of Electron-Deficient N-Heteroarenes with Aromatic Grignard Reagents", 《J. ORG. CHEM.》 *
FENG GAO ET AL.: "Room-temperature palladium-catalyzed direct 2-arylation of benzoxazoles with aryl and heteroaryl bromides", 《CHEM. COMMUN.》 *
JINYUN ZHANG ET AL.: "Synthesis, characterization and properties of aryl-fused bis-BN dihydropyrenes", 《CHEM. COMMUN.》 *
JOYDEV K. LAHA ET AL.: "Palladium-Catalyzed Intramolecular Oxidative Arylations for the Synthesis of Fused Biaryl Sulfones", 《ACS OMEGA》 *
KANDASAMY RAJAGURU ET AL.: "An efficient desulfitative C-C cross coupling of fused thiazolidine-2-thione with boronic acids and boronic acid pinacol esters: formation of fused thiazoles", 《RSC ADV.》 *
TAKEHIKO NISHIO ET AL.: "Photoaddition Reactions of Benzoxazole-2(3H)-thiones to Cycloalkenes and Heteroaromatics", 《HELVETICA CHIMICA ACTA》 *
TALEAH M. LEVESQUE ET AL.: "A palladium-catalyzed C-H functionalization route to ketones via the oxidative coupling of arenes with carbon monoxide", 《CHEM. SCI.》 *
XIN WANG ET AL.: "A Monophosphine Ligand Derived from Anthracene Photodimer: Synthetic Applications for Palladium-Catalyzed Coupling Reactions", 《ORG. LETT.》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022262310A1 (zh) * 2021-06-17 2022-12-22 广东阿格蕾雅光电材料有限公司 Btbf芳胺衍生物的合成方法
WO2024119296A1 (en) * 2022-12-05 2024-06-13 Boe Technology Group Co., Ltd. Emissive material, light-emitting diode, and display apparatus
CN115960064A (zh) * 2023-01-15 2023-04-14 西安交通大学 一种荧光发射材料及有机电致发光器件

Also Published As

Publication number Publication date
CN113861143B (zh) 2023-12-12

Similar Documents

Publication Publication Date Title
CN113861143B (zh) 一种热激活延迟荧光深蓝光材料及其制备方法与有机电致发光器件
CN110862381B (zh) 一种有机电致发光化合物及其制备方法和应用
CN102229623B (zh) 螺芴氧杂蒽磷氧类电致磷光主体材料及其合成和应用方法
CN115403580B (zh) 一种含氮杂环化合物及其用途
US10937971B2 (en) Organic monomolecular white light material, manufacturing method for the same, and OLED element
CN109678875A (zh) 一种磷光化合物和使用该化合物的有机发光二极管器件
CN109369660A (zh) 有机发光材料及其制法和含该材料的有机电致发光器件
CN109836436B (zh) 一种二噻吩化合物及其制备和应用
CN108558768A (zh) 一种含咪唑结构的屈类化合物及其有机发光器件
CN111454279A (zh) 一种有机电致发光化合物及其制备方法和应用
CN106188141B (zh) 一种oled材料及其应用
JPH07101911A (ja) 新規なピレン誘導体ならびにその製造方法
CN110551154A (zh) 一种含磷双环化合物及其制备方法和应用
CN111454265B (zh) 一种稠杂环化合物及其制备方法和应用
CN111574536B (zh) 一种有机电致发光化合物及其制备方法和应用
TWI397516B (zh) 含聯三伸苯基之芳香族化合物及有機發光二極體
CN111320615A (zh) 一类基于s,s-二氧-二苯并噻吩和菲并咪唑的小分子及其在电致发光器件中的应用
CN113861172B (zh) 基于苯并五元杂环的双极性荧光材料及其制备方法与有机电致发光器件
CN111039930A (zh) 双n-苯基-3-咔唑取代的菲并咪唑类化合物及其制备方法和作为电致发光器件的应用
CN107325103B (zh) 一种有机电致发光材料、其制备方法及应用
CN112979623B (zh) 一种五元杂环基化合物及其制备方法，有机电致发光器件及元件
CN108689986B (zh) 一种蒽类发光材料及其制备方法和应用
CN111116670A (zh) 一种有机金属铱配合物及其制备方法与应用
CN108752348A (zh) 一种杂环化合物及其有机电致发光器件
CN110467545B (zh) 一种蒽衍生物及其制备方法和应用

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