[go: up one dir, main page]

CN106800528A - 一种萘醌并9,9,10,10‑四甲基‑蒽类有机电致发光材料及其制备方法和应用 - Google Patents

一种萘醌并9,9,10,10‑四甲基‑蒽类有机电致发光材料及其制备方法和应用 Download PDF

Info

Publication number
CN106800528A
CN106800528A CN201611149861.1A CN201611149861A CN106800528A CN 106800528 A CN106800528 A CN 106800528A CN 201611149861 A CN201611149861 A CN 201611149861A CN 106800528 A CN106800528 A CN 106800528A
Authority
CN
China
Prior art keywords
compound
tetramethyl
substituted
preparation
organic electroluminescent
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
CN201611149861.1A
Other languages
English (en)
Other versions
CN106800528B (zh
Inventor
李庆
胡葆华
石宇
王岩
邹广辉
潘峰
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.)
Valiant Co Ltd
Original Assignee
Valiant Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Valiant Co Ltd filed Critical Valiant Co Ltd
Priority to CN201611149861.1A priority Critical patent/CN106800528B/zh
Publication of CN106800528A publication Critical patent/CN106800528A/zh
Application granted granted Critical
Publication of CN106800528B publication Critical patent/CN106800528B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/46—Phenazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/36—[b, e]-condensed, at least one with a further condensed benzene ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • 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
    • 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
    • C07D471/12—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 three hetero rings
    • C07D471/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/056—Ortho-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/147—Ortho-condensed systems the condensed system containing one ring with oxygen as ring hetero atom and two rings with nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/153—Ortho-condensed systems the condensed system containing two rings with oxygen as ring hetero atom and one ring with nitrogen as ring hetero atom
    • 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
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • 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
    • 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
    • H10K85/657—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
    • 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
    • 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)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明公开了一种萘醌并9,9,10,10‑四甲基‑蒽类有机电致发光材料及其制备方法和应用，上述有机电致发光材料结构式如式(Ⅰ)或式(Ⅱ)所示：。本发明提供的萘醌并9,9,10,10‑四甲基‑蒽类有机电致发光材料应用于OLED发光器件中，使得器件的电流效率、功率效率和外量子效率均得到很大改善。本发明提供的萘醌并9,9,10,10‑四甲基‑蒽类有机电致发光材料具有良好的应用效果，具有良好的产业化前景。

Description

一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料及其 制备方法和应用
技术领域
本发明涉及有机电致发光材料领域，尤其涉及一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料及其制备方法和应用。
背景技术
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品，也可以用于制作新型照明产品，有望替代现有的液晶显示和荧光灯照明，应用前景十分广泛。
OLED发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。作为电流器件，当对OLED发光器件的两端电极施加电压，并通过电场作用有机层功能材料膜层中的正负电荷，正负电荷进一步在发光层中复合，即产生OLED电致发光。
有机发光二极管(OLEDs)在大面积平板显示和照明方面的应用引起了工业界和学术界的广泛关注。然而，传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。外量子效率普遍低于5％，与磷光器件的效率还有很大差距。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间窜越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达100％。但磷光材料存在价格昂贵，材料稳定性较差，器件效率滚落严重等问题限制了其在OLEDs的应用。热激活延迟荧光(TADF)材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(△EST)，三线态激子可以通过反系间窜越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子，器件的内量子效率可以达到100％。同时，材料结构可控，性质稳定，价格便宜无需贵重金属，在OLEDs领域的应用前景广阔。
虽然理论上TADF材料可以实现100％的激子利用率，但实际上存在如下问题:(1)设计分子的T1和S1态具有强的CT特征,非常小的S1-T1态能隙,虽然可以通过TADF过程实现高T1→S1态激子转化率，但同时导致低的S1态辐射跃迁速率，因此，难于兼具(或同时实现)高激子利用率和高荧光辐射效率；(2)即使已经采用掺杂器件减轻T激子浓度猝灭效应，大多数TADF材料的器件在高电流密度下效率滚降严重。
就当前OLED显示照明产业的实际需求而言，目前OLED材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有的OLED材料存在的上述问题，现提供一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料及其制备方法和应用，旨在提供一种具有良好光电性能的有机电致发光材料，以满足面板制造企业的要求。
具体技术方案如下：
本发明的第一个方面是提供一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料，具有这样的特征，上述有机电致发光材料以萘醌并9,9,10,10-四甲基-蒽为母核结构，其结构式如式(Ⅰ)或式(Ⅱ)所示：
其中，Ar选自芳香取代基团；
其中，R1选自含取代基或不含取代基的含取代基或不含取代基的其中，X1选自氧原子、硫原子、二(C1-10直链烷基)取代的季烷基(或叔烷基)、二(C1-10支链烷基)取代的季烷基(或叔烷基)、芳基取代的季烷基(或叔烷基)、烷基取代的叔胺基或芳基取代的叔胺基中的一种。
上述的有机电致发光材料，还具有这样的特征，含取代基的和含取代基的为任一苯环或各苯环中被C6-20芳基、 一元取代，其中，X2、X3、X4分别独立地选自氧原子、硫原子、二(C1-10直链烷基)取代的季烷基(或叔烷基)、二(C1-10支链烷基)取代的季烷基(或叔烷基)、芳基取代的季烷基(或叔烷基)、烷基取代的叔胺基或芳基取代的叔胺基中的一种。
上述的有机电致发光材料，还具有这样的特征，含取代基的和含取代基的为任一苯环或各苯环中被 邻位一元取代，即上述取代基通过C1-C2、C2-C3、C3-C4、C1'-C2'、C2'-C3'或C3'-C4'键连接。
上述的有机电致发光材料，还具有这样的特征，Ar选自苯基、C1-10直链烷基取代的苯基、C1-10支链烷基取代的苯基、二联苯基、三联苯基、萘基、蒽基、菲基或苯并菲基中的一种。
上述的有机电致发光材料，还具有这样的特征，X1、X2、X3和X4分别独立地选自氧原子、硫原子、硒原子、二(C1-10直链烷基)取代的季碳、二(C1-10支链烷基)取代的季碳、芳基取代的季烷基、甲基取代的叔胺基或芳基取代的叔胺基中的一种。
优选的，本发明中R1优选为如下中的一种：
优选的，本发明中上述有机电致发光材料为如下化合物1-153中的任意一个：
以上为一些具体的结构形式，但本发明中提供的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料不局限于所列的这些化学结构，凡是以式(Ⅰ)或式(Ⅱ)为基础，取代基为定义的所有范围内基团的简单变换的化合物都应包含在内。
本发明的第二个方面是提供上述有机电致发光材料的制备方法，具有这样的特征，包括：
1)式(Ⅰ)化合物的制备
向反应瓶中装入称取的2-溴萘醌并9,9,10,10-四甲基-蒽、胺基化合物，加入反应溶剂，再加入催化剂和碱，在惰性气氛下，将上述反应物的混合溶液于110-150℃反应10-24小时，停止反应后经冷却、过滤、柱层析，得到式(Ⅰ)所示的有机电致发光材料，本发明中式(Ⅰ)所示的部分化合物的合成
2)式(Ⅱ)化合物的制备
向反应瓶中装入称取的萘醌并9,9,10,10-四甲基-蒽硼酸化合物、溴代化合物，加入反应溶剂，再加入催化剂和碱，在惰性气氛下，将上述反应物的混合溶液于100-110℃反应10-24小时，停止反应后经冷却、过滤、柱层析，得到式(Ⅱ)所示的有机电致发光材料，本发明中式(Ⅱ)所示的部分化合物的
优选的，式(Ⅰ)化合物的制备中，2-溴萘醌并9,9,10,10-四甲基-蒽与-胺基化合物的摩尔比为1:(1.0-1.5)。
优选的，式(Ⅰ)化合物的制备中，催化剂选自Pd(OAc)2、P(t-Bu)3或1，2-双环己基膦-2',6'-二甲氧基联苯中的一种或几种，优选为Pd(OAc)2和P(t-Bu)3，优选的，Pd(OAc)2与2-溴萘醌并9,9,10,10-四甲基-蒽的摩尔比为(0.005-0.01):1，P(t-Bu)3与2-溴萘醌并9,9,10,10-四甲基-蒽的摩尔比为(0.01-0.02):1。
优选的，碱选自叔丁醇钠、叔丁醇钾、甲醇钠、甲醇钾或碳酸钾中的一种，优选为叔丁醇钠，并且，叔丁醇钠与2-溴萘醌并9,9,10,10-四甲基-蒽的摩尔比为(2.0-4.0):1。
优选的，式(Ⅱ)化合物的制备中，9,10-二氢-9,9,10,10-四甲基-蒽硼酸化合物与溴代化合物的摩尔比为1:(1.0-1.5)。
优选的，催化剂选自Pd(OAc)2、P(t-Bu)3或1，2-双环己基膦-2',6'-二甲氧基联苯中的一种或几种，优选为Pd(OAc)2和1，2-双环己基膦-2',6'-二甲氧基联苯，并且，Pd(OAc)2与萘醌并9,9,10,10-四甲基-蒽硼酸化合物的摩尔比为(0.005-0.01):1，2-双环己基膦-2',6'-二甲氧基联苯与萘醌并9,9,10,10-四甲基-蒽硼酸化合物的摩尔比为(0.01-0.02):1。
优选的，碱选自叔丁醇钠、叔丁醇钾、甲醇钠、甲醇钾或碳酸钾中的一种，优选为碳酸钾，并且，碳酸钾与萘醌并9,9,10,10-四甲基-蒽硼酸化合物的摩尔比为(2.0-4.0):1。
上述制备方法中，反应溶剂均选自但不限于甲苯、二甲苯、均三甲苯中的一种或几种。
需要说明的是，本领域的技术人员在上述技术方案的基础上应可以合理的选择、量取溶剂。
本发明的第三个方面是提供上述有机电致发光材料在制备有机电致发光器件中的应用。
本发明的第四个方面是提供一种有机电致发光器件，该有机电致发光器件中含有多个功能层，还具有这样的特征，至少有一个功能层含有上述的有机电致发光材料。
本发明中所制备的有机电致发光器件一般包括依次叠加的ITO导电玻璃衬底、空穴传输层、发光层(涉及本发明中提供的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料)、电子传输层、电子注入层(LiF)和阴极层(Al)，所有功能层均采用真空蒸镀工艺制成。
应当理解，本发明中制作OLED器件的目的，只是为了更好地说明，本发明中提供的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料所具有的电致发光能力，而并非是对本发明所提供的有机电致发光材料的应用范围的限制。
上述方案的有益效果是：
本发明提供的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料应用于OLED发光器件中，使得器件的电流效率、功率效率和外量子效率均得到很大改善。本发明提供的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料具有良好的应用效果，具有良好的产业化前景。
附图说明
图1为本发明的实施例中提供的有机电致发光器件的结构示意图，由下层至上层，依次为透明基板层(1)、透明电极层(2)、空穴注入层(3)、空穴传输层(4)、发光层(5)、电子传输层(6)、电子注入层(7)、阴极反射电极层(8)，其中，发光层(5)涉及到本发明中所提供的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
下面结合附图和具体实施例对本发明作进一步说明，但不作为本发明的限定。
实施例1化合物1的制备
250mL的三口瓶，在通入氮气的气氛下，加入0.012mol(2.00g)咔唑，0.01mol(4.45g)化合物M1，0.03mol(2.88g)叔丁醇钠，10-4mol(23mg)Pd(OAc)2，2×10-4mol(0.4g)P(t-Bu)310％的甲苯溶液，100mL甲苯，加热回流10小时，取样点板，原料反应完全；自然冷却至室温(20-25℃)，过滤，收集滤液进行减压旋蒸(-0.09MPa，85℃)，进行柱层析，得到目标产物，纯度99％，收率63％。
元素分析结构(分子式C38H29NO2)：理论值C,85.85；H,5.50；N,2.63；O,6.02测试值：C,85.84；H,5.52；N,2.60；O,6.04。
HPLC-MS：材料理论值为531.22，实际值532.13。
实施例2化合物4的制备
化合物4的制备方法同实施例1，不同之处在于采用原料M2替换咔唑。
元素分析结构(分子式C42H31NO2)：理论值C,86.72；H,5.37；N,2.41；O,5.50测试值：C,86.70；H,5.38；N,2.42；O,5.50。
HPLC-MS：材料理论值为581.23，实际值582.20。
实施例3化合物8的制备
250mL的三口瓶，在通入氮气的气氛下，加入0.012mol(3.09g)化合物M3，0.01mol(4.45g)化合物M1，0.03mol(2.88g)叔丁醇钠，10-4mol(23mg)Pd(OAc)2，2×10-4mol(0.4g)P(t-Bu)310％的甲苯溶液，100mL邻二甲苯，加热回流10小时，取样点板，原料反应完全；自然冷却至室温(20-25℃)，过滤，收集滤液进行减压旋蒸(-0.09MPa，110℃)，进行柱层析，得到目标产物，纯度99％，收率52％。
元素分析结构(分子式C44H31NO3)：理论值C,85.00；H,5.03；N,2.25；O,7.72测试值：C,85.01；H,5.00；N,2.27；O,7.72。
HPLC-MS：材料理论值为621.23，实际值622.13。
实施例4化合物10的制备
化合物10的制备方法同实施例3，不同之处在于采用原料M4替换M3。
元素分析结构(分子式C47H37NO2)：理论值C,87.14；H,5.76；N,2.16；O,4.94测试值：C,87.15；H,5.74；N,2.15；O,4.96。
HPLC-MS：材料理论值为647.28，实际值648.19。
实施例5化合物11的制备
化合物11的制备方法同实施例4，不同之处在于采用原料M5替换M3。
元素分析结构(分子式C50H36N2O2)：理论值C,86.18；H,5.21；N,4.02；O,4.59测试值：C,86.20；H,5.22；N,4.00；O,4.58。
HPLC-MS：材料理论值为696.27，实际值696.22。
实施例6化合物33的制备
250mL的三口瓶，在通入氮气的气氛下，加入0.012mol(4.79g)化合物M6，0.01mol(4.45g)化合物M1，0.03mol(2.88g)叔丁醇钠，10-4mol(23mg)Pd(OAc)2，2×10-4mol(0.4g)P(t-Bu)310％的甲苯溶液，150mL均三甲苯，加热回流10小时，取样点板，原料反应完全；自然冷却至室温(20-25℃)，过滤，收集滤液进行减压旋蒸(-0.09MPa，150℃)，进行柱层析，得到目标产物，纯度99％，收率67％。
元素分析结构(分子式C56H45NO2)：理论值C,88.04；H,5.94；N,1.83；O,4.19测试值：C,88.03；H,5.97；N,1.82；O,4.18。
HPLC-MS：材料理论值为763.34，实际值762.40。
实施例7化合物45的制备
化合物45的制备方法同实施例6，不同之处在于采用原料M7替换M6。
元素分析结构(分子式C50H33NO4)：理论值C,84.37；H,4.67；N,1.97；O,8.99；测试值：C,84.35；H,4.66；N,2.00；O,8.99。
HPLC-MS：材料理论值为711.24，实际值712.24。
实施例8化合物54的制备
化合物54的制备方法同实施例6，不同之处在于采用原料M8替换M6。
元素分析结构(分子式C53H42N2O2)：理论值C,86.15；H,5.73；N,3.79；O,4.33；测试值：C,86.18；H,5.72；N,3.78；O,4.32。
HPLC-MS：材料理论值为738.32，实际值739.24。
实施例9化合物61的制备
化合物61的制备方法同实施例6，不同之处在于采用原料M9替换M6。
元素分析结构(分子式C53H42N2O2)：理论值C,86.15；H,5.73；N,3.79；O,4.33；测试值：C,86.16；H,5.72；N,3.77；O,4.35。
HPLC-MS：材料理论值为738.32，实际值739.33。
实施例10化合物65的制备
化合物65的制备方法同实施例6，不同之处在于采用原料M10替换M6。
元素分析结构(分子式C68H55N3O2)：理论值C,86.32；H,5.86；N,4.44；O,3.38；测试值：C,86.31；H,5.88；N,4.43；O,3.38。
HPLC-MS：材料理论值为945.43，实际值945.50。
实施例11化合物67的制备
化合物67的制备方法同实施例3，不同之处在于采用原料9,9-二甲基吖啶替换M3。
元素分析结构(分子式C41H35NO2)：理论值C,85.83；H,6.15；N,2.44；O,5.58；测试值：C,85.85；H,6.13；N,2.46；O,5.56。
HPLC-MS：材料理论值为573.27，实际值574.16
实施例12化合物69的制备
化合物69的制备方法同实施例3，不同之处在于采用原料吩噁嗪替换M3。
元素分析结构(分子式C38H29NO3)：理论值C,83.34；H,5.34；N,2.56；O,8.76；测试值：C,83.35；H,5.33；N,2.55；O,8.77。
HPLC-MS：材料理论值为547.21，实际值548.22。
实施例13化合物70的制备
化合物70的制备方法同实施例3，不同之处在于采用原料吩噻嗪替换M3。
元素分析结构(分子式C38H29NO2S)：理论值C,80.97；H,5.19；N,2.48；O,5.68；S,5.69；测试值：C,80.96；H,5.20；N,2.45；O,5.67；S,5.72。
HPLC-MS：材料理论值为563.19，实际值564.11。
实施例14化合物79的制备
化合物79的制备方法同实施例3，不同之处在于采用原料M11替换M3。
元素分析结构(分子式C47H37NO2S)：理论值C,83.03；H,5.49；N,2.06；O,4.71；S,4.72；测试值：C,83.04；H,5.48；N,2.08；O,4.70；S,4.70。
HPLC-MS：材料理论值为679.25，实际值679.21。
实施例15化合物96的制备
化合物96的制备方法同实施例6，不同之处在于采用原料M12替换M6。
元素分析结构(分子式C53H42N2O2)：理论值C,86.15；H,5.73；N,3.79；O,4.33；测试值：C,86.14；H,5.72；N,3.80；O,4.33。
HPLC-MS：材料理论值为738.32，实际值738.29。
实施例16化合物115的制备
化合物115的制备方法同实施例6，不同之处在于采用原料M13替换M6。
元素分析结构(分子式C50H36N2O3)：理论值C,84.25；H,5.09；N,3.93；O,6.73；测试值：C,84.24；H,5.10；N,3.92；O,6.74。
HPLC-MS：材料理论值为712.27，实际值713.30。
实施例17化合物136的制备
化合物136的制备方法同实施例6，不同之处在于采用原料M14替换M6。
元素分析结构(分子式C46H33NO3)：理论值C,85.29；H,5.13；N,2.16；O,7.41；测试值：C,85.31；H,5.12；N,2.17；O,7.40。
HPLC-MS：材料理论值为647.24，实际值648.19。
实施例18化合物139的制备
250mL的三口瓶，在通入氮气的气氛下，加入0.01mol(3.22g)9-(4-溴苯基)-咔唑，0.01mol(4.12g)化合物M1硼酸，0.03mol(4.14g)碳酸钾，10-4mol(23mg)Pd(OAc)2，2×10-4mol(84mg)2-双环己基膦-2',6'-二甲氧基联苯(S-phos)，100mL甲苯，100mL水。加热回流10小时，取样点板，原料反应完全；自然冷却至室温(20-25℃)，分液，保留有机相，过滤，收集滤液进行减压旋蒸(-0.09MPa，110℃)，进行柱层析，得到目标产物，纯度99％，收率78％。
元素分析结构(分子式C44H33NO2)：理论值C,86.96；H,5.47；N,2.30；O,5.27；测试值：C,86.97；H,5.47；N,2.31；O,5.25。
HPLC-MS：材料理论值为607.25，实际值608.24。
实施例19化合物141的制备
化合物141的制备方法同实施例18，不同之处在于采用原料M15替换9-(4-溴苯基)-咔唑。
元素分析结构(分子式C53H41NO2)：理论值C,87.94；H,5.71；N,1.93；O,4.42；测试值：C,87.95；H,5.72；N,1.92；O,4.41。
HPLC-MS：材料理论值为723.31，实际值724.22。
实施例20化合物142的制备
化合物142的制备方法同实施例18，不同之处在于采用原料M16替换9-(4-溴苯基)-咔唑。
元素分析结构(分子式C56H40N2O2)：理论值C,87.02；H,5.22；N,3.62；O,4.14；测试值：C,87.04；H,5.19；N,3.63；O,4.14。
HPLC-MS：材料理论值为772.31，实际值773.24。
实施例21化合物146的制备
化合物146的制备方法同实施例18，不同之处在于采用原料M17替换9-(4-溴苯基)-咔唑。
元素分析结构(分子式C47H39NO2)：理论值C,86.87；H,6.05；N,2.16；O,4.92；测试值：C,86.88；H,6.07；N,2.14；O,4.91。
HPLC-MS：材料理论值为649.29，实际值650.33。
上述制备获得的化合物2、146以及现有材料CBP的热性能、发光光谱及HOMO能级的测试结果如下表所示：
化合物 Tg(℃) Td(℃) Φm(％) HOMO能级(ev)
化合物12 157 420 495 80.6 -5.85
化合物146 150 414 500 78.6 -5.75
材料CBP 113 353 369 26.1 -5.9
由上表数据可知，本发明提供的化合物具有合适的HOMO能级以及较高的热稳定性，适合作为发光层的主体材料；同时，本发明所提供的化合物具有合适的发光光谱和较高的Φm，使得应用本发明所提供的化合物作为掺杂材料的OLED器件效率和寿命得到提升。
有机电致发光器件实施例
本发明的实施例22-31中以部分上述有机电致发光材料制备获得器件1-10，应当理解，器件实施过程与结果，只是为了更好地解释本发明，并非对本发明的限制，上述有机电致发光器件的制备方法如下：
a)对ITO阳极层(膜厚为150nm)依次进行碱洗涤、纯水洗涤、干燥，再进行紫外线-臭氧洗涤以清除透明ITO阳极层2表面的有机残留物。
b)在ITO阳极层上蒸镀空穴注入层(MoO3)，膜厚为10nm；
c)在空穴注入层上蒸镀空穴传输层(TAPC)，膜厚140nm；
d)在空穴传输层上蒸镀发光层(本发明提供的化合物：Ir(pq)2acac＝100：5(wt:wt)，膜厚30nm；
e)在发光层上蒸镀电子传输层(TPBI)，膜厚为50nm；
f)在电子传输层上蒸镀电子注入层装置(LiF)，膜厚1nm；
g)在电子注入层上蒸镀阴极反射电极层(Al)，膜厚80nm。
上述有机电致发光器件的制备方法中，TAPC、Ir(pq)2acac、TPBI、CBP的结构式如下所示：
如上完成器件1-10及对比器件后，用公知的驱动电路将阳极和阴极连接起来，测量器件的电流效率，发光光谱以及器件的寿命，器件1-10及对比器件1的主要结构层及测试结果如下表所示：
上述测试中，器件测试性能以比较例1作为参照，比较例1器件各项性能指标设为1.0。比较例1的电流效率为14.8cd/A(@10mA/cm2)；CIE色坐标为(0.66,0.33)；3000亮度下LT95寿命衰减为11Hr，驱动电压为4.5v(@10mA/cm2)。寿命测试系统为本发明的所有权人和上海大学共同开发的OLED器件寿命测试仪。
本发明的实施例32-37中以部分上述有机电致发光材料制备获得器件11-16，器件11-16的制备工艺与器件1-10的制备方法相同，区别在于发光层结构不同，如上完成器件11-16及对比器件2后，用公知的驱动电路将阳极和阴极连接起来，测量器件的电流效率，发光光谱以及器件的寿命，器件11-16及对比器件2的主要结构层及测试结果如下表所示：
实施例 器件 发光层结构(wt:wt) 电流效率 色彩 驱动电压
32 11 CBP:化合物1＝100:7 1.8 绿光 0.81
33 12 CBP:化合物11＝100:7 2.2 绿光 0.70
34 13 CBP:化合物96＝100:7 2.0 绿光 0.77
35 14 CBP:化合物141＝100:7 1.5 绿光 0.90
36 15 CBP:化合物142＝100:7 2.1 绿光 0.78
37 16 CBP:化合物146＝100:7 1.4 绿光 0.72
对比例2 对比器件2 CBP：GD19＝100:7 1.0 绿光 1.0
其中，GD19的结构式为：
由上表分析可知，本发明所提供的化合物无论作为发光层主体材料还是掺杂材料，所制得的OLED发光器件的效率及启动电压均比已知OLED材料获得较大改观，特别是器件高电流密度下的效率滚降获得改善。本发明所提供的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
以上所述仅为本发明较佳的实施例，并非因此限制本发明的实施方式及保护范围，对于本领域技术人员而言，应当能够意识到凡运用本发明说明书及图示内容所作出的等同替换和显而易见的变化所得到的方案，均应当包含在本发明的保护范围内。

Claims (9)

1.一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料，其特征在于，所述有机电致发光材料以萘醌并9,9,10,10-四甲基-蒽为母核结构，其结构式如式(Ⅰ)或式(Ⅱ)所示：
其中，Ar选自芳香取代基团；
其中，R1选自含取代基或不含取代基的含取代基或不含取代基的其中，X1选自氧原子、硫原子、二(C1-10直链烷基)取代的季烷基、二(C1-10支链烷基)取代的季烷基、芳基取代的季烷基、烷基取代的叔胺基或芳基取代的叔胺基中的一种。
2.根据权利要求1所述的有机电致发光材料，其特征在于，所述含取代基的和所述含取代基的为任一苯环或各苯环中被C6-20的芳基、一元取代，其中，X2、X3、X4分别独立地选自氧原子、硫原子、二(C1-10直链烷基)取代的季烷基、二(C1-10支链烷基)取代的季烷基、芳基取代的季烷基、烷基取代的叔胺基或芳基取代的叔胺基中的一种。
3.根据权利要求1所述的有机电致发光材料，其特征在于，所述Ar选自苯基、C1-10直链烷基取代的苯基、C1-10支链烷基取代的苯基、二联苯基、三联苯基、萘基、蒽基、菲基或苯并菲基中的一种。
4.根据权利要求2所述的有机电致发光材料，其特征在于，所述X1、所述X2、所述X3和所述X4分别独立地选自氧原子、硫原子、硒原子、二(C1-10直链烷基)取代的季碳、二(C1-10支链烷基)取代的季碳、芳基取代的季烷基、甲基取代的叔胺基或芳基取代的叔胺基中的一种。
5.一种根据权利要求1-4任一项所述的有机电致发光材料的制备方法，其特征在于，包括：
1)式(Ⅰ)化合物的制备
向反应瓶中装入称取的2-溴萘醌并9,9,10,10-四甲基-蒽、胺基化合物，加入反应溶剂，再加入催化剂和碱，在惰性气氛下，将上述反应物的混合溶液于110-150℃反应10-24小时，停止反应后经冷却、过滤、柱层析，得到式(Ⅰ)所示的有机电致发光材料；
2)式(Ⅱ)化合物的制备
向反应瓶中装入称取的萘醌并9,9,10,10-四甲基-蒽硼酸化合物、溴代化合物，加入反应溶剂，再加入催化剂和碱，在惰性气氛下，将上述反应物的混合溶液于100-110℃反应10-24小时，停止反应后经冷却、过滤、柱层析，得到式(Ⅱ)所示的有机电致发光材料。
6.根据权利要求5所述的制备方法，其特征在于，式(Ⅰ)化合物的制备中，所述2-溴萘醌并9,9,10,10-四甲基-蒽与所述胺基化合物的摩尔比为1:(1.0-1.5)；所述催化剂为Pd(OAc)2和P(t-Bu)3，并且，所述Pd(OAc)2与所述2-溴萘醌并9,9,10,10-四甲基-蒽的摩尔比为(0.005-0.01):1，所述P(t-Bu)3与所述2-溴萘醌并9,9,10,10-四甲基-蒽的摩尔比为(0.01-0.02):1；所述碱为叔丁醇钠，并且，所述碱与所述2-溴萘醌并9,9,10,10-四甲基-蒽的摩尔比为(2.0-4.0):1。
7.根据权利要求5所述的制备方法，其特征在于，式(Ⅱ)化合物的制备中，所述9,10-二氢-9,9,10,10-四甲基-蒽硼酸化合物与所述溴代化合物的摩尔比为1:(1.0-1.5)；所述催化剂为Pd(OAc)2和1，2-双环己基膦-2',6'-二甲氧基联苯，并且，所述Pd(OAc)2与所述萘醌并9,9,10,10-四甲基-蒽硼酸化合物的摩尔比为(0.005-0.01):1，所述2-双环己基膦-2',6'-二甲氧基联苯与所述萘醌并9,9,10,10-四甲基-蒽硼酸化合物的摩尔比为(0.01-0.02):1；所述碱为碳酸钾，并且，所述碱与所述萘醌并9,9,10,10-四甲基-蒽硼酸化合物的摩尔比为(2.0-4.0):1。
8.一种根据权利要求1-4任一项所述的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料在制备有机电致发光器件中的应用。
9.一种有机电致发光器件，包括多个功能层，其特征在于，至少有一个所述功能层含有权利要求1-4任一项所述的萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料。
CN201611149861.1A 2016-12-14 2016-12-14 一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料及其制备方法和应用 Active CN106800528B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611149861.1A CN106800528B (zh) 2016-12-14 2016-12-14 一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611149861.1A CN106800528B (zh) 2016-12-14 2016-12-14 一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料及其制备方法和应用

Publications (2)

Publication Number Publication Date
CN106800528A true CN106800528A (zh) 2017-06-06
CN106800528B CN106800528B (zh) 2019-06-28

Family

ID=58984905

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611149861.1A Active CN106800528B (zh) 2016-12-14 2016-12-14 一种萘醌并9,9,10,10-四甲基-蒽类有机电致发光材料及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN106800528B (zh)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0999256A1 (en) * 1998-05-01 2000-05-10 TDK Corporation Compounds for organic el element and organic el element
CN1747943A (zh) * 2003-02-14 2006-03-15 出光兴产株式会社 杂多环化合物,以及由其制备的色素、颜料、染料、变色材料组合物和变色薄膜
WO2011053035A2 (ko) * 2009-11-02 2011-05-05 (주)씨에스엘쏠라 유기발광화합물 및 이를 구비한 유기발광소자
KR20120070468A (ko) * 2010-12-21 2012-06-29 (주)씨에스엘쏠라 디하이드로안트라센계 유도체 및 이를 이용한 유기 광소자
WO2012093852A2 (ko) * 2011-01-04 2012-07-12 주식회사 두산 유기발광 화합물 및 이를 포함한 유기 전계발광 소자
KR101324787B1 (ko) * 2011-05-19 2013-10-31 (주)씨에스엘쏠라 유기발광화합물 및 이를 이용한 유기 광소자
TW201504392A (zh) * 2013-06-21 2015-02-01 Univ Kyushu Nat Univ Corp 紅色發光材料、有機發光元件及化合物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0999256A1 (en) * 1998-05-01 2000-05-10 TDK Corporation Compounds for organic el element and organic el element
CN1747943A (zh) * 2003-02-14 2006-03-15 出光兴产株式会社 杂多环化合物,以及由其制备的色素、颜料、染料、变色材料组合物和变色薄膜
WO2011053035A2 (ko) * 2009-11-02 2011-05-05 (주)씨에스엘쏠라 유기발광화합물 및 이를 구비한 유기발광소자
KR20120070468A (ko) * 2010-12-21 2012-06-29 (주)씨에스엘쏠라 디하이드로안트라센계 유도체 및 이를 이용한 유기 광소자
WO2012093852A2 (ko) * 2011-01-04 2012-07-12 주식회사 두산 유기발광 화합물 및 이를 포함한 유기 전계발광 소자
KR101324787B1 (ko) * 2011-05-19 2013-10-31 (주)씨에스엘쏠라 유기발광화합물 및 이를 이용한 유기 광소자
TW201504392A (zh) * 2013-06-21 2015-02-01 Univ Kyushu Nat Univ Corp 紅色發光材料、有機發光元件及化合物

Also Published As

Publication number Publication date
CN106800528B (zh) 2019-06-28

Similar Documents

Publication Publication Date Title
CN110407829B (zh) 一种芳胺类化合物及其有机发光器件
TWI611003B (zh) 用於電子裝置之化合物類
WO2017215549A1 (zh) 一种有机电致发光化合物及其应用
CN105418485B (zh) 一种新的绿光主体化合物及其制备方法和应用
CN105254561A (zh) 一种用于oled的含芴有机化合物及其应用
CN109748909A (zh) 一种含螺氧杂蒽芴和含氮六元杂环的化合物、其制备方法及其在有机电致发光器件中的应用
CN111004201B (zh) 有机电致发光化合物、其制备方法及有机电致发光器件
CN110386894A (zh) 一种空穴传输材料及其应用
CN111662190A (zh) 一种含芘或氮杂芘的有机化合物及其应用
WO2019196948A1 (zh) 一种以芳基酮为核心的化合物、其制备方法及其在oled上的应用
CN107056701A (zh) 一种基于双取代基‑9‑芴酮的化合物及其应用
CN116574118A (zh) 一种含杂原子和环烷基的有机化合物及包含其的有机电致发光器件
TWI641598B (zh) 化合物及其有機電子裝置
WO2023138254A1 (zh) 杂环化合物、有机电致发光材料及元件
CN110655504B (zh) 一种以二苯并环庚烯为核心的化合物及其在有机电致发光器件上的应用
CN106432158A (zh) 一种有机发光化合物材料及其应用
WO2019085759A1 (zh) 一种以氮杂螺芴和芳基酮为核心的化合物、其制备方法及其在oled上的应用
WO2023093829A1 (zh) 化合物与发光器件、显示装置
CN116874509A (zh) 一种含硼非对称结构多环化合物及包含其的有机电致发光器件
CN108148048A (zh) 以氮杂苯为核心的化合物及其在有机电致发光器件上的应用
CN107840841A (zh) 一种咔唑吡啶衍生物及其用途和有机电致发光器件
CN102850320A (zh) 含二苯并噻吩砜化合物及其制备方法和应用
CN106467511A (zh) 一种以吖啶酮为核心的化合物及其在有机电致发光器件上的应用
CN113461592B (zh) 一种联苯咔唑双三芳胺类有机化合物及其应用
CN115583888A (zh) 一种萘基取代芳胺化合物及其应用

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