WO2022088911A1 - 一种苯并菲衍生物及其应用 - Google Patents

一种苯并菲衍生物及其应用 Download PDF

Info

Publication number
WO2022088911A1
WO2022088911A1 PCT/CN2021/115226 CN2021115226W WO2022088911A1 WO 2022088911 A1 WO2022088911 A1 WO 2022088911A1 CN 2021115226 W CN2021115226 W CN 2021115226W WO 2022088911 A1 WO2022088911 A1 WO 2022088911A1
Authority
WO
WIPO (PCT)
Prior art keywords
atoms
groups
aromatic
group
heteroaromatic ring
Prior art date
Application number
PCT/CN2021/115226
Other languages
English (en)
French (fr)
Inventor
曹建华
姜坤
李程辉
程友文
王庆一
赵佳
王美艳
孙建波
Original Assignee
北京八亿时空液晶科技股份有限公司
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 北京八亿时空液晶科技股份有限公司 filed Critical 北京八亿时空液晶科技股份有限公司
Publication of WO2022088911A1 publication Critical patent/WO2022088911A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • 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
    • C07D487/02—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
    • C07D487/06—Peri-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
    • C07D491/12—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
    • C07D491/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/16—Peri-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
    • 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
    • C07D495/06—Peri-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
    • C07D495/12—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 three hetero rings
    • C07D495/16—Peri-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
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • 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
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—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
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—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
    • C09K2211/1044—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
    • C09K2211/1044—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
    • C09K2211/1059—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention belongs to the technical field of organic electroluminescence, and particularly relates to a triphenylene derivative and an application thereof.
  • organic electroluminescent elements Most of the substances used in organic electroluminescent elements are pure organics or organometallic complexes in which organics and metals form complexes, which can be divided into hole injectors, hole transporters, light-emitting materials, and electron transporters according to their applications. , electron injection, etc.
  • organic substances with relatively small ionization energy are mainly used as the hole injector or hole transporter
  • organic substances with high electronegativity are mainly used as the electron injector or electron transporter.
  • the substance used as the light-emitting auxiliary layer preferably satisfies the following characteristics.
  • the materials used in organic electroluminescent elements need good thermal stability. The reason is that Joule heat occurs in the organic electroluminescent element due to the migration of charges. At present, as a hole transport layer, it is usually used. The glass transition temperature of the material is low, so the phenomenon that the luminous efficiency decreases due to crystallization occurs when driving at a low temperature.
  • the organic matter adjacent to the cathode and the anode needs to be designed to have a small charge injection barrier and a high charge mobility.
  • the interface between the electrode and the organic layer and the interface between the organic layer and the organic layer always have energy barriers and inevitably accumulate some charges, so it is necessary to use a substance with excellent electrochemical stability.
  • the light-emitting layer is composed of two substances, a host light-emitting body and a dopant.
  • the dopant needs to have a high quantum efficiency.
  • the host light-emitting body needs to have a larger energy gap, so that energy transfer to the dopant is easy to occur.
  • Displays used for TVs, mobile devices, etc. realize full color according to the three primary colors of red, green, and blue, and the light-emitting layer is composed of red host emitters/dopants, green host emitters/dopants, and blue host emitters/dopants, respectively. dopant composition. At present, blue light materials still have the problems of low luminescence quantum efficiency and poor color purity.
  • the present invention provides a triphenylene derivative and its application.
  • the triphenylene derivative of the present invention is applied to organic electroluminescent materials, which can improve the organic electroluminescence Efficiency and life of light-emitting elements.
  • the first object of the present invention provides a kind of triphenylene derivative, and the structural formula of described triphenylene derivative is shown in formula (I):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , T 1 , T 2 are each independently selected from hydrogen, deuterium, straight-chain alkyl with C 1 -C 40 , with C 1 - C 40 straight chain heteroalkyl, C 3 -C 40 branched or cyclic alkyl, C 3 -C 40 branched or cyclic heteroalkyl, C 2 -C 40 alkene
  • Each group in can be substituted by one or more groups R;
  • G is C(R) 2 , NR, oxygen or sulfur
  • Z is the same or different at each occurrence, selected from CR or N, and ⁇ indicates adjacent groups X 1 , X 2 in formula (I) ;
  • Ar1 is the same or different at each occurrence and is selected from aromatic or heteroaromatic ring systems having 5 to 30 atoms, which may be substituted by one or more non-aromatic groups R8 ; here The two groups Ar 1 bound to the same nitrogen or phosphorus atom can also be bridged to each other by a single bond or a bridging group selected from N(R 8 ), C(R 8 ) 2 , oxygen or sulfur;
  • R 8 is selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, aliphatic hydrocarbon group with C 1 -C 20 , aromatic ring or heteroaromatic ring system with 5 to 30 atoms, wherein one or more hydrogen Atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R 8 may form with each other a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , T 1 , T 2 are each independently selected from hydrogen, deuterium, alkyl groups with C 1 -C 40 , alkyl groups with C 3 -C 40 branched or cyclic alkyl group, one of aromatic ring systems or heteroaromatic ring systems with 5 to 60 atoms, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , each of T 1 , T 2 may be substituted with one or more groups R.
  • the R is the same or different at each occurrence, and is selected from a hydrogen atom, a deuterium atom, a halogen atom, a nitrile group, N(Ar 1 ) 2 , a straight-chain alkyl group with C 1 -C 40 , a group with C 1 -C 40 straight chain heteroalkyl, branched or cyclic alkyl with C 3 -C 40 , branched or cyclic heteroalkyl with C 3 -C 40 , with C 2 -C 40 alkenyl or alkynyl, aromatic or heteroaromatic ring systems having 5 to 80, preferably 5 to 60, atoms;
  • Ar1 is the same or different at each occurrence and is selected from aromatic or heteroaromatic ring systems having 5 to 30 atoms, which may be substituted by one or more non-aromatic groups R8 ; here The two groups Ar 1 bound to the same nitrogen or phosphorus atom can also be bridged to each other by a single bond or a bridging group selected from N(R 8 ), C(R 8 ) 2 , oxygen or sulfur;
  • R 8 is selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, aliphatic hydrocarbon group with C 1 -C 20 , aromatic ring or heteroaromatic ring system with 5 to 30 atoms, wherein one or more hydrogen Atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R 8 may form with each other a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system.
  • Aryl in the sense of the present invention contains 6 to 60 carbon atoms
  • heteroaryl in the sense of the present invention contains 2 to 60 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5 ; the heteroatom is preferably selected from N, O or S.
  • Aryl or heteroaryl here is taken to mean simple aromatic rings, i.e., benzene, naphthalene, etc., or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc., or fused aryl or heteroaryl groups bases, such as anthracene, phenanthrene, quinoline, isoquinoline, etc.
  • Aromatic rings connected to each other by single bonds, such as biphenyls are on the contrary not referred to as aryl or heteroaryl groups, but as aromatic ring systems.
  • An aromatic or heteroaromatic ring system in the sense of the present invention is intended to be taken to mean a system which does not necessarily have to contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups can also consist of non-aromatic units For example C, N, O or S atoms are attached.
  • aryl or heteroaryl groups can also consist of non-aromatic units For example C, N, O or S atoms are attached.
  • two or more aryl groups are linked by, for example, short alkyl groups, such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine
  • Systems of diaryl ethers and the like are also taken to mean aromatic ring systems in the sense of the present invention.
  • aliphatic hydrocarbon radicals or alkyl radicals or alkenyl radicals or alkynyl radicals which contain from 1 to 40 carbon atoms in the sense of the present invention and in which individual hydrogen atoms or -CH 2 - radicals can also be substituted by the aforementioned radicals are preferably considered to be Refers to the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, hep
  • the alkoxy groups preferably have 1 to 40 carbon atoms are considered to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy base, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-heptyloxy Octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy.
  • Heteroalkyl groups preferably have 1 to 40 carbon atoms, and refer to groups in which individual hydrogen atoms or -CH 2 - groups may be replaced by oxygen, sulfur, halogen atoms, and are considered to mean alkoxy, Alkylthio, fluoroalkoxy, fluoroalkylthio, especially methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy Oxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio group, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroethy
  • cycloalkyl, cycloalkenyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl , cycloheptenyl, wherein one or more -CH2- groups can be replaced by the above-mentioned groups; in addition, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms or nitrile groups.
  • aromatic or heteroaromatic ring atoms according to the invention, aromatic or heteroaromatic ring systems which in each case may also be substituted by the abovementioned radicals R 8 in particular refer to radicals derived from benzene, Naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, benzene, terphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, trimerindene, heterotrimerindene, spirotrimerindene, spiroheterotrimerin
  • the structures of the triphenylene derivatives mainly include CJHB271 ⁇ CJHB480, wherein G is selected from oxygen, sulfur, CH 2 , C(CH 3 ) 2 , C(C 6 H 5 ) 2 , N-CH 3 , one of NC 2 H 5 , NC 6 H 5 :
  • the second object of the present invention is to provide an application of the triphenylene derivative in an organic electroluminescent material.
  • the organic electroluminescent material is a material for an organic electroluminescent element, a material for an organic field effect transistor or a material for an organic thin film solar cell.
  • the organic electroluminescent material may be constituted by using the triphenylene derivative of the present invention alone, or may contain other compounds simultaneously.
  • the third object of the present invention is to provide an organic electroluminescence device, the organic electroluminescence device includes a first electrode, a second electrode, and at least one electrode disposed between the first electrode and the second electrode. an organic layer, at least one organic layer contains the triphenylene derivative.
  • the organic electroluminescent device includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also contain other layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, excitation layers Sub-blocking layer, electron blocking layer and/or charge generating layer. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that each of these layers does not have to be present.
  • the organic electroluminescent device described herein may comprise one light-emitting layer, or it may comprise multiple light-emitting layers.
  • various light-emitting compounds capable of emitting light are used in the light-emitting layer.
  • Particular preference is given to systems having three emitting layers, wherein the three layers can exhibit blue, green and red emission. If more than one light-emitting layer is present, according to the present invention, at least one of these layers comprises a compound of the present invention.
  • the organic electroluminescent device does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, ie the light emitting layer and the hole injection layer or The anode is directly adjacent, and/or the light emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode.
  • organic electroluminescent devices which are characterized in that one or more layers are applied by means of a sublimation method, wherein the vacuum sublimation device is passed through at an initial pressure of less than 10 ⁇ 5 Pa, preferably less than 10 ⁇ 6 Pa Vapor deposition to apply the material.
  • the initial pressure may also be even lower, eg below 10 ⁇ 7 Pa.
  • a particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is thus structured.
  • organic electroluminescent devices from solution, for example by spin coating, or by means of any desired printing method such as screen printing, flexographic printing, lithographic printing, photoinduced thermography, thermal transfer printing, spraying Ink printing or nozzle printing to create one or more layers.
  • Soluble compounds are obtained, for example, by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers.
  • hybrid methods in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapour deposition.
  • the invention also relates to a method for producing an organic electroluminescent device according to the invention, characterized in that at least one layer is applied by means of a sublimation method, and/or characterized in that it is applied by means of an organic vapour deposition method or by means of sublimation of a carrier gas At least one layer is applied, and/or characterized in that the at least one layer is applied from solution by spin coating or by means of printing methods.
  • the present invention relates to containing at least one fused-ring aromatic compound of the present invention as indicated above.
  • the fused-ring aromatic compound may preferably contain other compounds in addition.
  • Processing the fused-ring aromatic compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires a formulation of the compounds according to the invention.
  • These formulations can be, for example, solutions, dispersions or emulsions.
  • mixtures of two or more solvents may preferably be used.
  • Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, Tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2, 4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclo
  • the organic layer further includes one of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer, and a light emitting layer.
  • the light-emitting layer includes a dopant and a light-emitting host
  • the dopant includes the triphenylene derivative
  • the light-emitting host is the triphenylene derivative, naphthalene, anthracene , pyrene, perylene, phenanthrene, fluoranthene, One of benzanthracene and pentacene and their derivatives.
  • the mass ratio of the dopant to the light-emitting host is 1:99-50:50.
  • the triphenylene derivative of the present invention is a novel organic electroluminescent compound with condensed ring structures of indole, benzofuran, and benzothiphenanthrene, which increases intramolecular luminescence on the basis of triphenylene.
  • adjusting the substituent group increases molecular steric hindrance, weakens the ⁇ - ⁇ interaction between molecules, improves the internal quantum efficiency of the molecule, and has a shorter emission wavelength than existing compounds.
  • the triphenylene derivative hinders the formation of organic intermolecular exciter-excited complexes, and increases the internal electron density and stability. Therefore, the triphenylene derivative of the present invention is used to prepare an organic electroluminescent device.
  • the triphenylene derivative improves the solubility of the solution and solves the problems of productivity and cost of the process that the blue light material has in the past, and it is not a vapor deposition process in the original process. , but can also be used to prepare light-emitting layers in other solution processes.
  • FIG. 1 is a schematic diagram of a bottom emission example of the organic electroluminescence device of the present invention.
  • FIG. 2 is a schematic diagram of a top emission example of the organic electroluminescent device of the present invention.
  • test instruments and methods for performance testing of OLED materials and components are as follows:
  • Luminance and chromaticity coordinates tested with a spectral scanner PhotoResearch PR-715;
  • Life Test Use LTS-1004AC Life Test Device.
  • the preparation method of compound CJHB271 comprises the following steps:
  • Triisopropyl ester stirred for 30 minutes, raised to room temperature and reacted for 1 hour, added dropwise 50 mL of 1N dilute aqueous hydrochloric acid solution, stirred for 30 minutes, separated the organic phase, extracted the aqueous phase with dichloromethane, collected the organic phase, dried and filtered , the filtrate was concentrated to dryness under reduced pressure, and was separated and purified by silica gel column to obtain Int.-2 as a white solid with a yield of 92%.
  • the preparation method of compound CJHB387 comprises the following steps:
  • the first step preparation of compound Int.-5
  • the first step the preparation of compound Int.-11
  • the intermediate Int.-10 of 6.6mmol (referring to the synthetic method of embodiment 1, only replaces the p-chlorobromobenzene in the first step with bromobenzene to prepare the intermediate Int.-10) is dispersed in 100mL dry THF, in Under nitrogen protection, it was cooled to -78°C with liquid nitrogen, 3.2 mL of 2.5M tert-butyllithium was added dropwise, the reaction was stirred for 1 hour, and 10.0 mmol of trimethyl borate was added dropwise.
  • Example 4 Referring to the preparation method of Example 4, only the 2-chloro-4,6-diphenyl-1,3,5-triazine in the second step in Example 4 was replaced by different halogenated compounds, and other experimental parameters were routinely adjusted. .
  • the preparation method of compound CJHB413 comprises the following steps:
  • the first step preparation of compound Int.-13
  • the third step preparation of compound Int.-15
  • Example 6 Referring to the preparation method of Example 6, only the 4,4'-dimethyldiphenylamine in the fifth step in Example 6 was replaced by different amines, and other experimental parameters were routinely adjusted.
  • Example 4 Referring to the preparation method of Example 4, only the 2-chloro-4,6-diphenyl-1,3,5-triazine in the second step in Example 4 was replaced by different halogenated compounds, and other experimental parameters were routinely adjusted. .
  • an OLED element As shown in FIG. 1, an OLED element, the preparation method of the OLED element shown includes the following steps:
  • the glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonicated in an acetone/ethanol mixed solvent for 30 minutes, and baked in a clean environment until completely dry, Irradiate with UV light cleaner for 10 min and bombard the surface with a low energy cation beam.
  • the above-mentioned treated ITO glass substrate is placed in a vacuum chamber, evacuated to 1 ⁇ 10 -5 to 9 ⁇ 10 -3 Pa, and the compound DNTPD is continuously evaporated on the above-mentioned anode layer film as a hole injection layer. , the thickness of the vapor-deposited film is Continue to vapor-deposit NPD on the above-mentioned hole-injection layer to form a hole-transporting layer, and the vapor-deposited film thickness is
  • the triphenylene derivative in Test Example 1 was CJHB271-1, and the other light-emitting elements were prepared according to the method of Test Example 1.
  • the triphenylene derivative in Test Example 1 was CJHB271-4, and the other light-emitting elements were prepared according to the method of Test Example 1.
  • the triphenylene derivative in Test Example 1 was CJHB387-1, and the other light-emitting elements were prepared according to the method of Test Example 1.
  • the triphenylene derivative in Test Example 1 was CJHB387-4, and the other light-emitting elements were prepared according to the method of Test Example 1.
  • the triphenylene derivative in Test Example 1 was CJHB336-2, and the other light-emitting elements were prepared according to the method of Test Example 1.
  • the triphenylene derivative in Test Example 1 was CJHB413-2, and the other light-emitting elements were prepared according to the method of Test Example 1.
  • the triphenylene derivative in Test Example 1 was CJHB413-5, and the other light-emitting elements were prepared according to the method of Test Example 1.
  • test samples 1-7 and control sample 1 were tested, and the results are shown in Table 5.
  • 1 and 2 are schematic diagrams of a bottom emission example of the organic electroluminescent device of the present invention and a schematic diagram of a top emission example of the organic electroluminescent device of the present invention.
  • the organic electroluminescence device of the present invention can be used in wall-mounted TVs, flat panel displays, flat illuminators for lighting, etc., copiers, printers, backlights of liquid crystal displays, light sources for measuring instruments, etc., display panels, sign lamps, and the like.

Abstract

本发明涉及一种苯并菲衍生物及其应用，所述的苯并菲衍生物的结构式如式(I)所示。本发明所述的苯并菲衍生物具有吲哚、苯并呋喃、苯并噻吩并苯并菲的稠环结构的新型有机电致发光化合物，是在苯并菲的基础上增大分子内的电子密度，同时调整取代基团增大分子位阻、减弱分子间的π-π相互作用，提高分子的内量子效率，并且具有与现有的化合物相比更短的发光波长。同时，所述的苯并菲衍生物阻碍有机分子间激-激复合物的生成、增加内部电子密度和稳定性，因此，利用本发明所述的苯并菲衍生物制备有机电致发光器件的效果和寿命明显提高。

Description

一种苯并菲衍生物及其应用 技术领域
本发明属于有机电致发光技术领域，具体涉及一种苯并菲衍生物及其应用。
背景技术
有机电致发光元件所使用的物质大部分为纯有机物或有机物与金属形成络合物的有机金属络合物，根据用途可区分为空穴注入物、空穴输送物、发光物、电子输送物、电子注入物等。在此，作为空穴注入物或空穴输送物主要使用离子化能相对较小的有机物，作为电子注入物或电子输送物主要使用电负性较大的有机物。此外，作为发光辅助层所使用的物质最好能满足如下特性。
第一、有机电致发光元件中所使用的物质需较好的热稳定性，其原因是在有机电致发光元件内部因电荷的迁移而发生焦耳热，目前，作为空穴输送层通常所使用的材料的玻璃化温度低，因此在低温下驱动时出现因发生结晶化而引起发光效率降低的现象。第二、为了降低驱动电压，需要与阴极和阳极邻接的有机物设计成电荷注入势垒较小，电荷迁移率高。第三、电极和有机层的界面、有机层和有机层的界面上一直存在能量壁垒而不可避免地累积一些电荷，因此需要使用电化学稳定性优异的物质。
发光层由主发光体和掺杂物这两种物质构成，掺杂物需要量子效率高，与掺杂物相比主发光体需要能隙大而容易发生向掺杂物的能量转移。用于电视、移动设备等的显示器根据红色、绿色、蓝色这三原色实现全彩色，发光层分别由红色主发光体/掺杂物、绿色主发光体/掺杂物以及蓝色主发光体/掺杂物构成。目前蓝光材料仍然存在发光量子效率低、色纯度差的问题。造成这种状况的主要原因是因为蓝光来自于能隙较宽的能级间的跃迁，而宽禁带的有机化合物在进行分子设计时存在一定的困难，其次蓝光材料的体系中存在着较强的π-π键 相互作用，有着很强的电荷转移特性，从而使宽带隙中存在更多的无辐射弛豫通道，加剧了分子之间荧光淬灭，降低了蓝光体系的量子产率。因此设计合成综合性能优良的蓝光材料，将成为有机电致发光材料研究的重要课题。
鉴于以上原因，特提出本发明。
发明内容
为了解决现有技术存在的以上问题，本发明提供了一种苯并菲衍生物及其应用，本发明的所述的苯并菲衍生物应用与有机电致发光材料中，可以提高有机电致发光元件的效率、寿命。
本发明的第一目的，提供了一种苯并菲衍生物，所述的苯并菲衍生物的结构式如式(I)所示：
Figure PCTCN2021115226-appb-000001
其中，R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2各自独立地选自氢、氘、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5～60个原子的芳族环系或杂芳族环系中的一种，R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2中的每个基团可被一个或多个基团R取代；
优选的，T 1和T 2通过选自O、S、S(＝O)、S(＝O) 2、NR、C(R) 2、BR、PR、P(＝O)R、Si(R) 2的桥连基彼此桥连；
X 1、X 2如式(II)所示：
Figure PCTCN2021115226-appb-000002
其中，G为C(R) 2、NR、氧或硫，Z在每次出现时相同或不同，选自CR或N，并且^指示式(I)中的相邻基团X 1、X 2；
所述R在每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、硝基、N(Ar 1) 2、N(R 7) 2、C(＝O)Ar 1、C(＝O)R 7、P(＝O)(Ar 1) 2、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5至80个、优选5至60个原子的芳族环或杂芳族环系、具有5至60个原子的芳氧基或杂芳氧基中的一种，R中的每个基团可被一个或多个基团R 7取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 7C＝CR 7、C≡C、Si(R 7) 2、Ge(R 7) 2、Sn(R 7) 2、C＝O、C＝S、C＝Se、C＝NR 7、P(＝O)(R 7)、SO、SO 2、NR 7、O、S或CONR 7代替，并且其中一个或多个氢原子被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的R可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系，所述环系可被一个或多个基团R 7取代；
R 7在每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、硝基、N(Ar 1) 2、N(R 8) 2、C(＝O)Ar 1、C(＝O)R 8、P(＝O)(Ar 1) 2、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5至60个原子的芳族环或杂芳族环系、具有5至60个原子的芳氧基或杂芳氧基中的一种，R 7中的每个基团可被一个或多个基团R 8取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 8C＝CR 8、C≡C、Si(R 8) 2、Ge(R 8) 2、Sn(R 8) 2、C＝O、C＝S、C＝Se、C＝NR 8、P(＝O)(R 8)、SO、SO 2、NR 8、O、S或CONR 8代替，并且其中一个或多个氢原子可被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的取代基R可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳 族环系，所述环系可被一个或多个基团R 8取代；
Ar 1在每次出现时相同或不同，选自具有5～30个原子的芳族或杂芳族环系，所述环系可被一个或多个非芳族基团R 8取代；此处键合至同一氮原子或磷原子的两个基团Ar 1也可通过单键或选自N(R 8)、C(R 8) 2、氧或硫的桥连基彼此桥连；
R 8选自氢原子、氘原子、氟原子、腈基、具有C 1-C 20的脂族烃基、具有5～30个原子的芳族环或杂芳族环系，其中一个或多个氢原子可被氘原子、卤素原子、或腈基代替，其中两个或更多个相邻的取代基R 8可彼此形成单环或多环的脂族、芳族或杂芳族环系。
进一步地，所述R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2各自独立地选自氢、氘、具有C 1-C 40的烷基、具有C 3-C 40的支链或环状的烷基、具有5～60个原子的芳族环系或杂芳族环系中一种，R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2中的每个基团可被一个或多个基团R取代。
进一步地，所述R在每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、N(Ar 1) 2、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5至80个、优选5至60个原子的芳族环或杂芳族环系；
Ar 1在每次出现时相同或不同，选自具有5～30个原子的芳族或杂芳族环系，所述环系可被一个或多个非芳族基团R 8取代；此处键合至同一氮原子或磷原子的两个基团Ar 1也可通过单键或选自N(R 8)、C(R 8) 2、氧或硫的桥连基彼此桥连；
R 8选自氢原子、氘原子、氟原子、腈基、具有C 1-C 20的脂族烃基、具有5～30个原子的芳族环或杂芳族环系，其中一个或多个氢原子可被氘原子、卤素原子、或腈基代替，其中两个或更多个相邻的取代基R 8可彼此形成单环或多环的脂族、芳族或杂芳族环系。
本发明意义上的芳基含有6-60个碳原子，在本发明意义上的杂芳基含有2-60个碳原子和至少一个杂原子，其条件是碳原子和杂原子的总和至少是5；所述杂原子优选选自N、O或S。此处的芳基或杂芳基被认为是指简单的芳族 环，即苯、萘等，或简单的杂芳族环，如吡啶、嘧啶、噻吩等，或稠合的芳基或杂芳基，如蒽、菲、喹啉、异喹啉等。通过单键彼此连接的芳族环，例如联苯，相反地不被称为芳基或杂芳基，而是称为芳族环系。
在本发明意义上的芳族或杂芳族环系旨在被认为是指不必仅含有芳基或杂芳基的体系，而是其中多个芳基或杂芳基还可以由非芳族单元例如C、N、O或S原子连接。因此，例如，和其中两个或更多个芳基被例如短的烷基连接的体系一样，诸如芴、9,9’-螺二芴、9,9-二芳基芴、三芳基胺、二芳基醚等的体系也被认为是指在本发明意义上的芳族环系。
对于本发明意义上的含有1～40个碳原子并且其中单独的氢原子或-CH 2-基团还可被上述基团取代的脂族烃基或者烷基或者烯基或炔基优选被认为是指如下基团：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、新戊基、环戊基、正己基、新己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基或辛炔基。烷氧基优选具有1-40个碳原子的烷氧基被认为是指甲氧基、三氟甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、仲戊氧基、2-甲基丁氧基、正己氧基、环己氧基、正庚氧基、环庚氧基、正辛氧基、环辛氧基、2-乙基己氧基、五氟乙氧基和2,2,2-三氟乙氧基。杂烷基优选具有1-40个碳原子的烷基，是指其中单独的氢原子或-CH 2-基团可被氧、硫、卤素原子取代的基团，被认为是指烷氧基、烷硫基、氟代的烷氧基、氟代的烷硫基，特别是指甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、甲硫基、乙硫基、正丙硫基、异丙硫基、正丁硫基、异丁硫基、仲丁硫基、叔丁硫基、三氟甲硫基、三氟甲氧基、五氟乙氧基、五氟乙硫基、2,2,2-三氟乙氧基、2,2,2-三氟乙硫基、乙烯氧基、乙烯硫基、丙烯氧基、丙烯硫基、丁烯硫基、丁烯氧基、戊烯氧基、戊烯硫基、环戊烯氧基、环戊烯硫基、己烯氧基、己烯硫基、环己烯氧基、环己烯硫基、乙炔氧基、乙炔硫基、丙炔氧基、丙炔硫基、丁炔氧基、丁炔硫基、戊炔氧基、 戊炔硫基、己炔氧基、己炔硫基。
一般来说，根据本发明的环烷基、环烯基可为环丙基、环丁基、环戊基、环己基、环丁烯基、环戊烯基、环己烯基、环庚基、环庚烯基，其中一个或多个-CH2-基团可被上述基团代替；此外，一个或多个氢原子还可被氘原子、卤素原子或腈基代替。
根据本发明的芳族或杂芳族环原子，在每种情况下还可被上述基团R 8取代的芳族或杂芳族环系，特别是指衍生自如下物质的基团：苯、萘、蒽、苯并蒽、菲、芘、
Figure PCTCN2021115226-appb-000003
苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5,6]喹啉、苯并[6,7]喹啉、苯并[7,8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1,5-二氮杂蒽、2,7-二氮杂芘、2,3-二氮杂芘、1,6-二氮杂芘、1,8-二氮杂芘、4,5-二氮杂芘，4,5,9,10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-噁二唑、1,2,4-噁二唑、1,2,5-噁二唑、1,3,4-噁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、吲嗪和苯并噻二唑或者衍生自这些体系的组合的基团。
进一步地，所述的苯并菲衍生物的结构主要包括CJHB271～CJHB480，其中G选自氧、硫、CH 2、C(CH 3) 2、C(C 6H 5) 2、N-CH 3、N-C 2H 5、N-C 6H 5中的一种：
Figure PCTCN2021115226-appb-000004
Figure PCTCN2021115226-appb-000005
Figure PCTCN2021115226-appb-000006
Figure PCTCN2021115226-appb-000007
Figure PCTCN2021115226-appb-000008
Figure PCTCN2021115226-appb-000009
Figure PCTCN2021115226-appb-000010
Figure PCTCN2021115226-appb-000011
Figure PCTCN2021115226-appb-000012
Figure PCTCN2021115226-appb-000013
Figure PCTCN2021115226-appb-000014
Figure PCTCN2021115226-appb-000015
本发明的第二目的，提供了一种所述的苯并菲衍生物在有机电致发光材料中的应用。
进一步地，所述的有机电致发光材料为有机电致发光元件用材料、有机场效应晶体管用材料或有机薄膜太阳电池用材料。
有机电致发光材料可以单独使用本发明的苯并菲衍生物构成，也可以同时含有其他化合物。
本发明的第三目的，提供了一种有机电致发光装置，所述的有机电致发光装置包括第一电极、第二电极和置于所述第一电极和第二电极之间的至少一层有机层，至少一层有机层包含所述的苯并菲衍生物。
所述有机电致发光装置包含阴极、阳极和至少一个发光层。除了这些层之外，它还可以包含其它的层，例如在每种情况下，包含一个或多个空穴注入层、空穴传输层、空穴阻挡层、电子传输层、电子注入层、激子阻挡层、电子阻挡层和/或电荷产生层。具有例如激子阻挡功能的中间层同样可引入两个发光层之间。然而，应当指出，这些层中的每个并非必须都存在。此处所述有机电致发光装置可包含一个发光层，或者它可包含多个发光层。即，将能够发光的多种发光化合物用于所述发光层中。特别优选具有三个发光层的体系，其中所述三个层可显示蓝色、绿色和红色发光。如果存在多于一个的发光层，则根据本发 明，这些层中的至少一个层包含本发明的化合物。
进一步地，根据本发明的有机电致发光装置不包含单独的空穴注入层和/或空穴传输层和/或空穴阻挡层和/或电子传输层，即发光层与空穴注入层或阳极直接相邻，和/或发光层与电子传输层或电子注入层或阴极直接相邻。
在根据本发明的有机电致发光装置的其它层中，特别是在空穴注入和空穴传输层中以及在电子注入和电子传输层中，所有材料可以按照根据现有技术通常所使用的方式来使用。本领域普通技术人员因此将能够在不付出创造性劳动的情况下与根据本发明的发光层组合使用关于有机电致发光元件所知的所有材料。
此外优选如下的有机电致发光装置，其特征在于借助于升华方法施加一个或多个层，其中在真空升华装置中在低于10 -5Pa、优选低于10 -6Pa的初压下通过气相沉积来施加所述材料。然而，所述初压还可能甚至更低，例如低于10 -7Pa。
同样优选如下的有机电致发光器件，其特征在于借助于有机气相沉积方法或借助于载气升华来施加一个或多个层，其中，在10 -5Pa至1Pa之间的压力下施加所述材料。该方法的特别的例子是有机蒸气喷印方法，其中所述材料通过喷嘴直接施加，并且因此是结构化的。
此外优选如下的有机电致发光装置，从溶液中，例如通过旋涂，或借助于任何所希望的印刷方法例如丝网印刷、柔性版印刷、平版印刷、光引发热成像、热转印、喷墨印刷或喷嘴印刷，来产生一个或多个层。可溶性化合物，例如通过适当的取代获得可溶性化合物。这些方法也特别适于低聚物、树枝状大分子和聚合物。此外可行的是混合方法，其中例如从溶液中施加一个或多个层并且通过气相沉积施加一个或多个另外的层。
这些方法是本领域普通技术人员通常已知的，并且他们可以在不付出创造性劳动的情况下将其应用于包含根据本发明的化合物的有机电致发光元件。
因此，本发明还涉及制造根据本发明的有机电致发光装置的方法，其特征在于借助于升华方法来施加至少一个层，和/或特征在于借助于有机气相沉积方 法或借助于载气升华来施加至少一个层，和/或特征在于从溶液中通过旋涂或借助于印刷方法来施加至少一个层。
此外，本发明涉及包含至少一种上文指出的本发明的稠环芳香族化合物。如上文关于有机电致发光装置指出的相同优选情况适用于所述本发明的稠环芳香族化合物。特别是，所述稠环芳香族化合物此外还可优选包含其它化合物。从液相处理根据本发明的稠环芳香族化合物，例如通过旋涂或通过印刷方法进行处理，需要根据本发明的化合物的制剂。这些制剂可以例如是溶液、分散体或乳液。出于这个目的，可优选使用两种或更多种溶剂的混合物。合适并且优选的溶剂例如是甲苯，苯甲醚，邻二甲苯、间二甲苯或对二甲苯，苯甲酸甲酯，均三甲苯，萘满，邻二甲氧基苯，四氢呋喃，甲基四氢呋喃，四氢吡喃，氯苯，二噁烷，苯氧基甲苯，特别是3-苯氧基甲苯，(-)-葑酮，1,2,3,5-四甲基苯，1,2,4,5-四甲基苯，1-甲基萘，2-甲基苯并噻唑，2-苯氧基乙醇，2-吡咯烷酮，3-甲基苯甲醚，4-甲基苯甲醚，3,4-二甲基苯甲醚，3,5-二甲基苯甲醚，苯乙酮，α-萜品醇，苯并噻唑，苯甲酸丁酯，异丙苯，环己醇，环己酮，环己基苯，十氢化萘，十二烷基苯，苯甲酸乙酯，茚满，苯甲酸甲酯，1-甲基吡咯烷酮，对甲基异丙基苯，苯乙醚，1,4-二异丙基苯，二苄醚，二乙二醇丁基甲基醚，三乙二醇丁基甲基醚，二乙二醇二丁基醚，三乙二醇二甲基醚，二乙二醇单丁基醚，三丙二醇二甲基醚，四乙二醇二甲基醚，2-异丙基萘，戊苯，己苯，庚苯，辛苯，1,1-双(3,4-二甲基苯基)乙烷，或这些溶剂的混合物。
进一步地，所述的有机层还包括电子注入层、电子输送层、空穴阻挡层、电子阻挡层、空穴输送层、空穴注入层、发光层中的一种。
进一步地，所述的发光层包括掺杂物和发光主体，所述的掺杂物包括所述的苯并菲衍生物，所述的发光主体为所述的苯并菲衍生物、萘、蒽、芘、苝、菲、荧蒽、
Figure PCTCN2021115226-appb-000016
苯并蒽和并五苯及其衍生物中的一种。
进一步地，所述的掺杂物与发光主体的质量比为1:99～50:50。
与现有技术相比，本发明的有益效果为：
本发明所述的苯并菲衍生物具有吲哚、苯并呋喃、苯并噻吩并苯并菲的稠环结构的新型有机电致发光化合物，是在苯并菲的基础上增大分子内的电子密度，同时调整取代基团增大分子位阻、减弱分子间的π-π相互作用，提高分子的内量子效率，并且具有与现有的化合物相比更短的发光波长。同时，所述的苯并菲衍生物阻碍有机分子间激-激复合物的生成、增加内部电子密度和稳定性，因此，利用本发明所述的苯并菲衍生物制备有机电致发光器件的效果和寿命明显提高，此外，所述的苯并菲衍生物改善了对溶液的溶解度而解决以往蓝光材料所具有的工序的生产性以及费用的问题，并且在原有的工序中不是其蒸镀工序，而是在其他溶液工序中也可以用于制备发光层。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明的有机电致发光装置的一个底部发光例子的示意图；
图2是本发明的有机电致发光装置的一个顶部发光例子的示意图。
附图标记
1-基板、2-阳极、3-孔穴注入层、4-孔穴传输/电子阻挡层、5-发光层、6-孔穴阻挡/电子传输层、7-电子注入层、8-阴极。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明的技术方案进行详细的描述。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做出创造性劳动的前提下所得到的所有其它实施方式，都属于本发明所保护的范围。
下述对OLED材料及元件进行性能测试的测试仪器及方法如下：
OLED元件性能检测条件：
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；
电流密度和起亮电压：使用数字源表Keithley 2420测试；
功率效率：使用NEWPORT 1931-C测试；
寿命测试：使用LTS-1004AC寿命测试装置。
实施例1
化合物CJHB271的制备方法，包括如下步骤：
第一步：化合物Int.-1的制备
Figure PCTCN2021115226-appb-000017
在氮气保护下，24.5g(127.0mmol)的对氯溴苯溶于300mL干燥的四氢呋喃中，用液氮降温至-78℃，缓慢滴加入56.0mL的2.5M正丁基锂正己烷溶液，搅拌反应1小时，滴加入19.5g(140.0mmol)的对氯苯腈溶于50mL干燥四氢呋喃的溶液，升至室温搅拌反应2小时，加入50mL的饱和氯化铵水溶液，搅拌反应30分钟，分出有机相，水相用乙酸乙酯萃取，收集有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到27.7g白色固体，收率87％。
第二步：化合物Int.-2的制备
Figure PCTCN2021115226-appb-000018
在氮气保护下，12.6g(50.0mmol)第一步制备的Int.-1溶解于200mL的二氯甲烷中，冰水浴降温到0℃，加入20.0g的四溴化碳和12.5g的亚磷酸三异丙酯，搅拌反应30分钟，升到室温反应1小时，滴加入50mL的1N稀盐酸水溶液，搅拌30分钟，分出有机相，水相用二氯甲烷萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到白色固体Int.-2，收率92％。
第三步：化合物Int.-3的制备
Figure PCTCN2021115226-appb-000019
取20.0g(50.0mmol)第二步制备的中间体Int.-2与100mL的1,4-二氧六环混合，在氮气保护下，加入110.0mmol的苯并呋喃-2-硼酸或苯并噻吩-2-硼酸或1-取代吲哚-2-硼酸或1,1-取代的茚-2-硼酸和112.5mg的醋酸钯催化剂、410.5mg的2-双环己基膦-2’,6’-二甲氧基联苯以及80.0mmol的水合磷酸钾，再加入40mL的水，升温至60℃搅拌反应12小时，冷却到室温，加入100mL的乙酸乙酯和100mL的水，分出有机相，水相再用乙酸乙酯萃取，收集有机相再用饱和盐水洗，有机相干燥过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到白色固体Int.-3，收率60～65％。
第四步：化合物Int.-4的制备
Figure PCTCN2021115226-appb-000020
20.0mmol第三步制备的中间体Int-3和100mL的氯仿、20mL的硝基甲烷混合，再加入1.6g的无水氯化铁，加热回流反应24小时，冷却到室温，加入50mL稀盐酸水溶液，用二氯甲烷萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到中间体Int.-4，收率55～65％。
第五步：化合物CJHB271的制备
Figure PCTCN2021115226-appb-000021
将5.0mmol第四步制备的中间体Int.-4分散在60mL的甲苯中，加入12.0mmol的二苯胺，再加入1.5g(15.0mmol)的叔丁醇钠、55.0mg(0.05mmol)的Pd2(dba)3CHCl3催化剂和0.1mL的10％叔丁基磷甲苯溶液，升温至100℃搅拌反应12小时，反应结束后，加入50mL的水，分出有机相，水相用甲苯-THF萃取，收集有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，再用二氯甲烷和乙醇重结晶，得到CJHB271，黄色固体。实验数据如表1所示：
表1
Figure PCTCN2021115226-appb-000022
实施例2
化合物CJHB387的制备方法，包括如下步骤：
第一步：化合物Int.-5的制备
Figure PCTCN2021115226-appb-000023
在氮气保护下，12.8g(50.0mmol)的2,7-二甲氧基氧杂蒽-9-酮溶解于200mL的二氯甲烷中，冰水浴降温到0℃，加入20.0g的四溴化碳和12.5g的亚磷酸三异丙酯，搅拌反应30分钟，升到室温反应1小时，滴加入50mL的1N稀盐酸水溶液，搅拌30分钟，分出有机相，水相用二氯甲烷萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到白色固体Int.-5，收率94％。
第二步：化合物Int.-6的制备
Figure PCTCN2021115226-appb-000024
参照实施例1第三步的制备方法，仅将实施例1第三步中的Int.-2替换为中间体Int.-5，制备中间体Int.-6，收率80～90％。
第三步：化合物Int.-7的制备
Figure PCTCN2021115226-appb-000025
参照实施例1第四步的制备方法，仅将实施例1第四步中的Int.-3替换为中间体Int.-6，于室温搅拌反应12小时，制备中间体Int.-7，收率65～75％。
第四步：化合物Int.-8的制备
Figure PCTCN2021115226-appb-000026
在氮气保护下，20.0mmol的中间体Int.-7溶解于120mL干燥的二氯甲烷中，用液氮降温至-40℃，滴加入40.0mmol的三溴化硼溶于二氯甲烷的溶液，搅拌反应2小时，升到室温，滴加入50mL的1N稀盐酸水溶液，搅拌1小时，分出有机相，水相用二氯甲烷萃取，有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到固体Int.-8，收率90～94％。
第五步：化合物Int.-9的制备
Figure PCTCN2021115226-appb-000027
在氮气保护下，20.0mmol的中间体Int.-8溶解于120mL干燥的二氯甲烷中，加入60.0mmol的吡啶，用冰水浴降温至0℃，滴加入48.0mmol的三氟甲基磺酸酐溶于二氯甲烷的溶液，搅拌反应2小时，升到室温搅拌反应2小时，加入50mL的1N稀盐酸水溶液，分出有机相，水相用二氯甲烷萃取，有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到固体Int.-9，收率92～96％。
第六步：化合物CJHB387的制备
Figure PCTCN2021115226-appb-000028
将5.0mmol第五步制备的中间体Int.-9分散在60mL的甲苯中，加入12.0mmol的4,4’-二甲基二苯胺，再加入2.0g(20.0mmol)的叔丁醇钠、55.0mg(0.05 mmol)的Pd2(dba)3CHCl3催化剂和0.1mL的10％叔丁基磷甲苯溶液，升温至100℃搅拌反应12小时，反应结束后，加入50mL的水，分出有机相，水相用乙酸乙酯-THF萃取，收集有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，再用THF-甲苯重结晶，得到CJHB387，黄色固体。
实验数据如表2所示。
表2
Figure PCTCN2021115226-appb-000029
实施例3
化合物CJHB270～CJHB324、CJHB386、CJHB388～CJHB403的制备：
参照实施例1～2的制备方法，仅将不同的肿胺替换实施例1中第五步的二 苯胺或实施例2中第六步的4,4’-二甲基二苯胺，其他实验参数进行常规调整。
实施例4
化合物CJHB336的制备：
第一步：化合物Int.-11的制备
Figure PCTCN2021115226-appb-000030
6.6mmol的中间体Int.-10(参照实施例1的合成方法，仅将第一步中的对氯溴苯替换为溴苯制备中间体Int.-10)分散于100mL干燥的THF中，在氮气保护下，用液氮降温至-78℃，滴加入3.2mL的2.5M叔丁基锂，搅拌反应1小时，滴加入10.0mmol的硼酸三甲酯，反应1小时后，加入50mL的2N稀盐酸水溶液，分出有机相，水相用乙酸乙酯萃取，收集有机相干燥，过滤，滤液减压浓缩干，用石油醚洗涤，过滤，得到白色固体，收率65～75％。
第二步：化合物CJHB336的制备
Figure PCTCN2021115226-appb-000031
取5.0mmol第一步制备的中间体Int.-10与40mL的甲苯混合，在氮气保护下，加入4.0mmol的2-氯-4,6-二苯基-1,3,5-三嗪、10.0mmol的无水碳酸钾和58.0mg的Pd(PPh3)4催化剂，再加入20mL的乙醇和20mL的水，升温至回流搅拌反应12小时，冷却到室温，加入50mL的二氯甲烷和100mL的水，分出有机相，水相再用二氯甲烷萃取，收集有机相再用饱和盐水洗，有机相干燥过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到白色固体CJHB336，收率75～86％。
实验数据如表3所示。
表3
Figure PCTCN2021115226-appb-000032
实施例5
化合物CJHB325～CJHB335、CJHB337～CJHB385的制备：
参照实施例4的制备方法，仅将不同的卤代物替换实施例4中第二步的2-氯-4,6-二苯基-1,3,5-三嗪，其他实验参数进行常规调整。
实施例6
化合物CJHB413的制备方法，包括如下步骤：
第一步：化合物Int.-13的制备
Figure PCTCN2021115226-appb-000033
取22.0g(50.0mmol)的中间体Int.-12(参照实施例2的合成方法制备)与100mL的1,4-二氧六环混合，在氮气保护下，加入110.0mmol的苯并呋喃-3-硼酸或苯并噻吩-3-硼酸或1-取代吲哚-3-硼酸或1,1-取代的茚-3-硼酸和112.5mg的醋酸钯催化剂、410.5mg的2-双环己基膦-2’,6’-二甲氧基联苯以及80.0mmol的水合磷酸钾，再加入40mL的水，升温至60℃搅拌反应12小时，冷却到室温，加入100mL的乙酸乙酯和50mL的水，分出有机相，水相再用乙酸乙酯萃取，收集有机相再用饱和盐水洗，有机相干燥过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到中间体Int.-13，收率70～80％。
第二步：化合物Int.-14的制备
Figure PCTCN2021115226-appb-000034
在氮气保护下，10.5mmol第一步制备的中间体Int.-13溶解于200mL的二氯甲烷中，加入63.0mmol的碘，再加入10mL的环氧丙烷，用254nm的紫外灯照射，搅拌反应12小时，减压浓缩干，加入100mL的甲醇分散，过滤，滤饼用硅胶柱分离纯化，得到黄色固体中间体Int.-14，收率85～95％。
第三步：化合物Int.-15的制备
Figure PCTCN2021115226-appb-000035
参照实施例2第四步的合成方法，仅将实施例2第四步中的中间体Int.-7替换为中间体Int.-13，制备得到中间体Int.-15，收率92～96％。
第四步：化合物Int.-16的制备
Figure PCTCN2021115226-appb-000036
参照实施例2第五步的合成方法，仅将实施例2第五步中的中间体Int.-8替换为中间体Int.-15，制备得到中间体Int.-16，收率85～90％。
第五步：化合物CJHB413的制备
Figure PCTCN2021115226-appb-000037
将5.0mmol第四步制备的中间体Int.-16分散在60mL的甲苯中，加入12.0mmol的4,4’-二甲基二苯胺，再加入2.0g(20.0mmol)的叔丁醇钠、55.0mg(0.05mmol)的Pd2(dba)3CHCl3催化剂和0.1mmol的Xanphos，升温至90℃搅拌反应12小时，反应结束后，加入50mL的水，分出有机相，水相用乙酸乙酯-THF萃取，收集有机相干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，再用THF-甲苯重结晶，得到CJHB413，黄色固体。
实验数据如表4所示：
表4
Figure PCTCN2021115226-appb-000038
实施例7
化合物CJHB404～CJHB412、CJHB414～CJHB429的制备：
参照实施例6的制备方法，仅将不同的肿胺替换实施例6中第五步的4,4’-二甲基二苯胺，其他实验参数进行常规调整。
实施例8
化合物CJHB430～CJHB480的制备：
参照实施例4的制备方法，仅将不同的卤代物替换实施例4中第二步的2-氯-4,6-二苯基-1,3,5-三嗪，其他实验参数进行常规调整。
试验例1
如图1所示，一种OLED元件，所示的OLED元件的制备方法包括如下步骤：
1)将涂布了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。
2)把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10 -5～9×10 -3Pa，在上述阳极层膜上继续分别蒸镀化合物DNTPD作为空穴注入层，蒸镀膜厚为
Figure PCTCN2021115226-appb-000039
在上述空穴注入层膜上继续蒸镀NPD为空穴传输层，蒸镀膜厚为
Figure PCTCN2021115226-appb-000040
3)在空穴传输层上继续蒸镀一层化合物HT202作为电子阻挡层，蒸镀膜厚为
Figure PCTCN2021115226-appb-000041
4)在电子阻挡层上继续蒸镀一层实施例1-8制备的苯并菲衍生物CJHB271～CJHB480中的一种和BH011作为有机发光层，其中，BH011为主体材料和本发明所述的苯并菲衍生物为掺杂材料，所述的的苯并菲衍生物在BH011中的掺杂浓度为1～20％，蒸镀膜厚为
Figure PCTCN2021115226-appb-000042
5)在上述有机发光层上再继续蒸镀一层化合物TPBI作为空穴阻挡层，蒸镀膜厚为
Figure PCTCN2021115226-appb-000043
6)在上述空穴阻挡层上再继续蒸镀一层化合物LiQ和ET205作为器件的电子传输层，其中，LiQ和ET205的质量比为1:1，蒸镀膜厚为
Figure PCTCN2021115226-appb-000044
7)在上述空穴阻挡层上再继续蒸镀一层化合物LiF作为器件的电子传输层，蒸镀膜厚为
Figure PCTCN2021115226-appb-000045
最后，在上述电子传输层之上蒸镀金属铝作为元件的阴极层，蒸镀膜厚为
Figure PCTCN2021115226-appb-000046
其中，试验例1中所使用的化合物结构式如下所示：
Figure PCTCN2021115226-appb-000047
试验样品1
试验例1中的苯并菲衍生物为CJHB271-1，其他按照试验例1的方法制备的发光元件。
试验样品2
试验例1中的苯并菲衍生物为CJHB271-4，其他按照试验例1的方法制备的发光元件。
试验样品3
试验例1中的苯并菲衍生物为CJHB387-1，其他按照试验例1的方法制备的发光元件。
试验样品4
试验例1中的苯并菲衍生物为CJHB387-4，其他按照试验例1的方法制备的发光元件。
试验样品5
试验例1中的苯并菲衍生物为CJHB336-2，其他按照试验例1的方法制备的发光元件。
试验样品6
试验例1中的苯并菲衍生物为CJHB413-2，其他按照试验例1的方法制备的发光元件。
试验样品7
试验例1中的苯并菲衍生物为CJHB413-5，其他按照试验例1的方法制备的发光元件。
对照样品1
试验例1中的苯并菲衍生物替换为化合物BD10，其他按照试验例1的方法制备的发光元件，其中，化合物BD10的结构式如下所示：
Figure PCTCN2021115226-appb-000048
将试验样品1-7和对照样品1的发光元件的性能进行检测，结果如表5所示。
表5
Figure PCTCN2021115226-appb-000049
上表5中可以看出，在电流密度为10mA/cm 2条件下的驱动电压、半峰宽FWHM、电流效率以及在亮度为1000cd/m 2初始条件下的器件寿命LT90％的数据是针对对照样品1归一化。
结论：从性能测试结果表5可以看到，本发明的化合物作为蓝光染料获得了深蓝光有机电致发光器件，相较于采用BD10作为蓝光掺杂材料的有机电致发光器件，元件的电流效率更高、驱动电压降低，而且器件初始亮度在1000cd/m 2的条件下，器件的LT90％寿命也有了很大的改善。
图1和2是本发明的有机电致发光装置的一个底部发光例子的示意图与本发明的有机电致发光装置的一个顶部发光例子的示意图。
产业上的应用可能性
本发明的有机电致发光装置可以在壁挂电视、平板显示器、照明等的平面发光体、复印机、打印机、液晶显示器的背光源或计量仪器类等的光源，显示板、标识灯等中应用。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到 变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (10)

  1. 一种苯并菲衍生物，其特征在于，所述的苯并菲衍生物的结构式如式(I)所示：
    Figure PCTCN2021115226-appb-100001
    其中，R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2各自独立地选自氢、氘、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5～60个原子的芳族环系或杂芳族环系中的一种，R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2中的每个基团可被一个或多个基团R取代；
    优选的，T 1和T 2通过选自O、S、S(＝O)、S(＝O) 2、NR、C(R) 2、BR、PR、P(＝O)R、Si(R) 2的桥连基彼此桥连；
    X 1、X 2如式(II)所示：
    Figure PCTCN2021115226-appb-100002
    其中，G为C(R) 2、NR、氧或硫，Z在每次出现时相同或不同，选自CR或N，并且^指示式(I)中的相邻基团X 1、X 2；
    所述R在每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、 硝基、N(Ar 1) 2、N(R 7) 2、C(＝O)Ar 1、C(＝O)R 7、P(＝O)(Ar 1) 2、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5至80个、优选5至60个原子的芳族环或杂芳族环系、具有5至60个原子的芳氧基或杂芳氧基中的一种，R中的每个基团可被一个或多个基团R 7取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 7C＝CR 7、C≡C、Si(R 7) 2、Ge(R 7) 2、Sn(R 7) 2、C＝O、C＝S、C＝Se、C＝NR 7、P(＝O)(R 7)、SO、SO 2、NR 7、O、S或CONR 7代替，并且其中一个或多个氢原子被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的R可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系，所述环系可被一个或多个基团R 7取代；
    R 7在每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、硝基、N(Ar 1) 2、N(R 8) 2、C(＝O)Ar 1、C(＝O)R 8、P(＝O)(Ar 1) 2、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5至60个原子的芳族环或杂芳族环系、具有5至60个原子的芳氧基或杂芳氧基中的一种，R 7中的每个基团可被一个或多个基团R 8取代，或这些体系的组合，其中一个或多个非相邻的-CH 2-基团可被R 8C＝CR 8、C≡C、Si(R 8) 2、Ge(R 8) 2、Sn(R 8) 2、C＝O、C＝S、C＝Se、C＝NR 8、P(＝O)(R 8)、SO、SO 2、NR 8、O、S或CONR 8代替，并且其中一个或多个氢原子可被氘原子、卤素原子、腈基或硝基代替，其中两个或更多个相邻的取代基R可以任选地接合或稠合形成单环或多环的脂族、芳族或杂芳族环系，所述环系可被一个或多个基团R 8取代；
    Ar 1在每次出现时相同或不同，选自具有5～30个原子的芳族或杂芳族环系，所述环系可被一个或多个非芳族基团R 8取代；此处键合至同一氮原子或磷原子的两个基团Ar 1也可通过单键或选自N(R 8)、C(R 8) 2、氧或硫的桥连基彼此桥连；
    R 8选自氢原子、氘原子、氟原子、腈基、具有C 1-C 20的脂族烃基、具有5～30个原子的芳族环或杂芳族环系，其中一个或多个氢原子可被氘原子、卤素原子、 或腈基代替，其中两个或更多个相邻的取代基R 8可彼此形成单环或多环的脂族、芳族或杂芳族环系。
  2. 根据权利要求1所述的苯并菲衍生物，其特征在于，所述R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2各自独立地选自氢、氘、具有C 1-C 40的烷基、具有C 3-C 40的支链或环状的烷基、具有5～60个原子的芳族环系或杂芳族环系中一种，R 1、R 2、R 3、R 4、R 5、R 6、T 1、T 2中的每个基团可被一个或多个基团R取代。
  3. 根据权利要2所述的苯并菲衍生物，其特征在于，所述R在每次出现时相同或不同，选自氢原子、氘原子、卤素原子、腈基、N(Ar 1) 2、具有C 1-C 40的直链烷基、具有C 1-C 40的直链杂烷基、具有C 3-C 40的支链或环状的烷基、具有C 3-C 40的支链或环状的杂烷基、具有C 2-C 40的烯基或炔基、具有5至80个、优选5至60个原子的芳族环或杂芳族环系；
    Ar 1在每次出现时相同或不同，选自具有5～30个原子的芳族或杂芳族环系，所述环系可被一个或多个非芳族基团R 8取代；此处键合至同一氮原子或磷原子的两个基团Ar 1也可通过单键或选自N(R 8)、C(R 8) 2、氧或硫的桥连基彼此桥连；
    R 8选自氢原子、氘原子、氟原子、腈基、具有C 1-C 20的脂族烃基、具有5～30个原子的芳族环或杂芳族环系，其中一个或多个氢原子可被氘原子、卤素原子、或腈基代替，其中两个或更多个相邻的取代基R 8可彼此形成单环或多环的脂族、芳族或杂芳族环系。
  4. 根据权利要求1-3任意一项所述的苯并菲衍生物，其特征在于，所述的苯并菲衍生物的结构主要包括CJHB271～CJHB480，其中G选自氧、硫、CH 2、C(CH 3) 2、C(C 6H 5) 2、N-CH 3、N-C 2H 5、N-C 6H 5中的一种：
    Figure PCTCN2021115226-appb-100003
    Figure PCTCN2021115226-appb-100004
    Figure PCTCN2021115226-appb-100005
    Figure PCTCN2021115226-appb-100006
    Figure PCTCN2021115226-appb-100007
    Figure PCTCN2021115226-appb-100008
    Figure PCTCN2021115226-appb-100009
    Figure PCTCN2021115226-appb-100010
    Figure PCTCN2021115226-appb-100011
    Figure PCTCN2021115226-appb-100012
    Figure PCTCN2021115226-appb-100013
    Figure PCTCN2021115226-appb-100014
    Figure PCTCN2021115226-appb-100015
  5. 一种权利要求1-4任意一项所述的苯并菲衍生物在有机电致发光材料中的应用。
  6. 根据权利要求5所述的应用，其特征在于，所述的有机电致发光材料为有机电致发光元件用材料、有机场效应晶体管用材料或有机薄膜太阳电池用材料。
  7. 一种有机电致发光装置，其特征在于，所述的有机电致发光装置包括第一电极、第二电极和置于所述第一电极和第二电极之间的至少一层有机层，至少一层有机层包含权利要求1-4任意一项所述的苯并菲衍生物。
  8. 根据权利要求7所述的有机电致发光装置，其特征在于，所述的有机层还包括电子注入层、电子输送层、空穴阻挡层、电子阻挡层、空穴输送层、空穴注入层、发光层中的一种。
  9. 根据权利要求8所述的有机电致发光装置，其特征在于，所述的发光层包括掺杂物和发光主体，所述的掺杂物包括权利要求1-4任意一项所述的苯并菲衍生物，所述的发光主体为权利要求1-4任意一项所述的苯并菲衍生物、萘、蒽、芘、苝、菲、荧蒽、
    Figure PCTCN2021115226-appb-100016
    苯并蒽和并五苯及其衍生物中的一种。
  10. 根据权利要求9所述的有机电致发光装置，其特征在于，所述的掺杂物与发光主体的质量比为1:99～50:50。
PCT/CN2021/115226 2020-10-29 2021-08-30 一种苯并菲衍生物及其应用 WO2022088911A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011178673.8 2020-10-29
CN202011178673.8A CN112266387B (zh) 2020-10-29 2020-10-29 一种苯并菲衍生物及其应用

Publications (1)

Publication Number Publication Date
WO2022088911A1 true WO2022088911A1 (zh) 2022-05-05

Family

ID=74344876

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/115226 WO2022088911A1 (zh) 2020-10-29 2021-08-30 一种苯并菲衍生物及其应用

Country Status (3)

Country Link
CN (1) CN112266387B (zh)
TW (1) TWI808518B (zh)
WO (1) WO2022088911A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112266387B (zh) * 2020-10-29 2023-05-26 北京八亿时空液晶科技股份有限公司 一种苯并菲衍生物及其应用
CN116675706B (zh) * 2023-08-03 2023-12-01 吉林奥来德光电材料股份有限公司 一种噁唑并苯并咔唑磷光主体材料及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004083162A1 (ja) * 2003-03-20 2004-09-30 Idemitsu Kosan Co. Ltd. 芳香族アミン誘導体及びそれを用いた有機エレクトロルミネッセンス素子
US20160020408A1 (en) * 2013-03-07 2016-01-21 Duk San Neolux Co., Ltd. Compound for organic electric element, organic electric element comprising the same and electronic device thereof
CN110156824A (zh) * 2018-02-13 2019-08-23 北京绿人科技有限责任公司 有机发光化合物及其应用和有机电致发光器件
CN112266387A (zh) * 2020-10-29 2021-01-26 北京八亿时空液晶科技股份有限公司 一种苯并菲衍生物及其应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017186760A1 (en) * 2016-04-29 2017-11-02 Merck Patent Gmbh Materials for organic electroluminescent devices
CN110698430A (zh) * 2019-10-23 2020-01-17 苏州久显新材料有限公司 硫杂菲啶酮衍生物及其合成方法和含有硫杂菲啶酮衍生物的电子器件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004083162A1 (ja) * 2003-03-20 2004-09-30 Idemitsu Kosan Co. Ltd. 芳香族アミン誘導体及びそれを用いた有機エレクトロルミネッセンス素子
US20160020408A1 (en) * 2013-03-07 2016-01-21 Duk San Neolux Co., Ltd. Compound for organic electric element, organic electric element comprising the same and electronic device thereof
CN110156824A (zh) * 2018-02-13 2019-08-23 北京绿人科技有限责任公司 有机发光化合物及其应用和有机电致发光器件
CN112266387A (zh) * 2020-10-29 2021-01-26 北京八亿时空液晶科技股份有限公司 一种苯并菲衍生物及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE REGISTRY 7 October 2014 (2014-10-07), ANONYMOUS : "Benzo[a]benzo[1,2]carbazolo[3,4-c]carbazole (CA INDEX NAME) ", XP055926742, retrieved from STN Database accession no. 1628116-42-6 *

Also Published As

Publication number Publication date
CN112266387A (zh) 2021-01-26
CN112266387B (zh) 2023-05-26
TWI808518B (zh) 2023-07-11
TW202216655A (zh) 2022-05-01

Similar Documents

Publication Publication Date Title
WO2022088910A1 (zh) 一种咔唑衍生物及其应用
WO2022257584A1 (zh) 化合物和包含该化合物的有机电致发光装置和电子设备
CN113801151B (zh) 一种稠环芳香族化合物及其应用
WO2022213854A1 (zh) 一种咔唑衍生物及其应用
CN113735853B (zh) 一种有机金属配合物以及包含该金属配合物的电致发光元件和化合物配方
CN113234106A (zh) 一种四齿环金属配合物及有机发光装置
WO2022088911A1 (zh) 一种苯并菲衍生物及其应用
WO2022237407A1 (zh) 一种有机化合物、有机电致发光材料及其装置
WO2023065996A1 (zh) 蒽衍生物、有机电致发光材料、发光装置及消费型产品
WO2023231795A1 (zh) 一种杂环化合物及包含它的有机发光元件
WO2023151394A1 (zh) 一种芴衍生物及其应用
WO2024012522A1 (zh) 一种咔唑衍生物及其在oled中的应用
WO2023236982A1 (zh) 一种菲啶衍生物及及其应用
CN114044785A (zh) 一种含硼化合物和有机电致发光元件、有机电致发光材料
CN112876498A (zh) 多环芳族化合物和含有该多环芳族化合物的有机电致发光元件
CN112812108A (zh) 化合物及包含该化合物的有机电致发光装置
CN112812086B (zh) 有机金属络合物的辅助配体以及包括其的装置和调配物
TW201835075A (zh) 用於有機電致發光裝置之材料
CN112830902B (zh) 杂环螺芴化合物及其应用
CN112812023B (zh) 有机化合物、有机电致发光器件用材料、有机电致发光器件
CN114349798A (zh) 一种金属配合物与应用及消费型产品
CN113387821A (zh) 芴类化合物、有机电致发光元件及消费型产品
CN112794833B (zh) 一种蓝光染料化合物及其应用
CN113912636B (zh) 含硅杂环化合物和含有该化合物的有机电致发光元件
CN112794804B (zh) 螺芴衍生物及其应用

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: 21884643

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: 21884643

Country of ref document: EP

Kind code of ref document: A1