WO2018095382A1 - 芳香胺衍生物及其制备方法和用途 - Google Patents

芳香胺衍生物及其制备方法和用途 Download PDF

Info

Publication number
WO2018095382A1
WO2018095382A1 PCT/CN2017/112703 CN2017112703W WO2018095382A1 WO 2018095382 A1 WO2018095382 A1 WO 2018095382A1 CN 2017112703 W CN2017112703 W CN 2017112703W WO 2018095382 A1 WO2018095382 A1 WO 2018095382A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
atoms
substituted
ring
aromatic
Prior art date
Application number
PCT/CN2017/112703
Other languages
English (en)
French (fr)
Inventor
杨曦
潘君友
Original Assignee
广州华睿光电材料有限公司
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 广州华睿光电材料有限公司 filed Critical 广州华睿光电材料有限公司
Priority to CN201780059206.3A priority Critical patent/CN109790457B/zh
Priority to US16/463,653 priority patent/US11512039B2/en
Publication of WO2018095382A1 publication Critical patent/WO2018095382A1/zh

Links

Images

Classifications

    • 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
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—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
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • C07C2603/50—Pyrenes; Hydrogenated pyrenes
    • 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
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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 relates to the field of organic electroluminescence technology, in particular to an aromatic amine derivative, a mixture and a composition thereof, and the use thereof in the field of organic electroluminescence.
  • OLEDs Organic light-emitting diodes
  • Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic matter.
  • An organic electroluminescence device utilizing an organic electroluminescence phenomenon generally has a structure in which a positive electrode and a negative electrode and an organic layer are contained therebetween.
  • the organic layer has a multilayer structure, and each layer contains a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like may be included.
  • Such an organic electroluminescence device when a voltage is applied between the two electrodes, a hole is injected from the positive electrode into the organic layer, and a negative electrode is injected into the organic substance, and when the injected hole meets the electron, an exciton is formed. The excitons emit light when they transition back to the ground state.
  • Such an organic electroluminescence device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.
  • the development of a blue fluorescent material having a narrow-band emission spectrum and good stability is advantageous for obtaining a longer-life and higher-efficiency blue light device, and on the other hand, it is advantageous for the improvement of the color gamut, thereby improving the display effect.
  • the light-emitting layer of the prior art blue organic electroluminescent device adopts a host-guest doping structure.
  • the conventional blue light host material is a ruthenium-based fused ring derivative, as described in the patents CN1914293B, CN102448945B, US2015287928A1, etc.
  • these compounds have problems of insufficient luminous efficiency and brightness, and poor lifetime of the device.
  • an aryl vinylamine compound (WO 04/013073, WO 04/016575, WO 04/018587) can be used.
  • these compounds have poor thermal stability and are easily decomposed, resulting in poor lifetime of the device, which is currently the most important shortcoming in the industry.
  • the blue light-emitting materials can have deep blue light emission, and they are thermally stable, exhibit good efficiency and longevity in the organic electroluminescence element, are easy to repeat in the manufacture and operation of the device, and have simple material synthesis.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are the same or different from each other, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Or R 8 are each independently selected from: H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkane having 1 to 20 C atoms.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may form a single or multiple ring to each other and/or a ring to which the group is bonded Aliphatic or aromatic ring system;
  • One or more of the hydrogen atoms of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may be optionally substituted by a deuterium atom.
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II), and the others are independently selected. a: a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms;
  • one or more of the groups Ar 1 , Ar 2 , Ar 3 or Ar 4 may form a polycyclic aliphatic or aromatic ring system with each other and/or a ring bonded to the group;
  • One or more hydrogen atoms of the Ar 1 , Ar 2 , Ar 3 or Ar 4 may be further optionally substituted by a deuterium atom;
  • R 9 , R 10 , R 11 , R 12 or R 13 are the same or different from each other, and each of R 9 , R 10 , R 11 , R 12 and R 13 is independently selected from: H or has 1 to 20 C a linear alkyl group of an atom, or an alkoxy group having 1 to 20 C atoms, or a thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic group having 3 to 20 C atoms An alkyl group, or an alkoxy group having 3 to 20 C atoms, or a thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or having 1 to 20 C atoms Substituted keto group, or alkoxycarbonyl group having 2 to 20 C atoms, or aryloxycarbonyl group having 7 to 20 C atoms, cyano group, carbamoyl group, haloformyl group, formy
  • R 9 , R 10 , R 11 , R 12 or R 13 groups may form a monocyclic or polycyclic aliphatic or aromatic ring with respect to each other and/or a ring bonded to the group. system;
  • Ar 5 and Ar 6 are the same or different, and each of Ar 5 or Ar 6 is independently selected from: H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms. Or a thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or an alkoxy group having 3 to 20 C atoms, or having 3 a thioalkoxy group of up to 20 C atoms, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms Or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate,
  • One or more groups in Ar 5 and Ar 6 may form a polycyclic aliphatic or aromatic ring system with each other and/or a ring bonded to the group;
  • One or more hydrogen atoms of R 9 , R 10 , R 11 , R 12 , R 13 , Ar 5 , or Ar 6 may be further optionally substituted with a halogen atom;
  • a high polymer comprising at least one repeating unit selected from the above aromatic amine derivatives.
  • a composition comprising the above aromatic amine derivative or the above-mentioned high polymer, and at least one organic solvent.
  • a mixture comprising the above aromatic amine derivative or the above-mentioned high polymer, and at least one organic functional material selected from the group consisting of: hole (also called hole) injection or transport material (HIM/HTM) ), hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescent emitter), thermally excited delayed fluorescent material (TADF material) and organic dye.
  • hole also called hole injection or transport material
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix material Host
  • singlet illuminant fluorescent illuminant
  • triplet illuminant phosphorescent emitter
  • TADF material thermally excited delayed fluorescent material
  • An organic electroluminescent device comprising: a cathode, an anode, and an organic layer, wherein the organic layer is formed of the above aromatic amine derivative or the above polymer or the above composition or a mixture thereof.
  • the above aromatic amine derivative has a fluorescence emission having an emission wavelength at a short wavelength, and its luminescence spectrum exhibits a narrow half-peak width, so that the substance has a deep blue fluorescence emission and has high luminous efficiency.
  • the organic electroluminescent device prepared by such an aromatic amine derivative has dark blue color coordinates, high luminous efficiency, and long device lifetime.
  • 1 is a schematic diagram of an electronic device of an embodiment.
  • the host material In the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.
  • metal organic complexes metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • composition printing ink, ink, and ink have the same meaning and are interchangeable.
  • substitution of a hydrogen atom by a deuterium atom means that one or more hydrogen atoms in Ar 6 may or may not be substituted by a deuterium atom.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are the same or different from each other, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 Or R 8 are each independently selected from: H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thio group having 1 to 20 C atoms.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may form a single or multiple ring to each other and/or a ring to which the group is bonded Aliphatic or aromatic ring system;
  • One or more of the hydrogen atoms of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may be further optionally substituted with a halogen atom;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 are the same or different from each other; and R 1 , R 2 , R 3 , R 4 , R 5 R 6 , R 7 or R 8 are each independently selected from: H, or a linear alkyl group having 1 to 10 C atoms, or an alkoxy group having 1 to 10 C atoms, or 1 to 10 a thioalkoxy group of a C atom, or a branched or cyclic alkyl group having 3 to 10 C atoms, or an alkoxy group having 3 to 10 C atoms, or sulfur having 3 to 10 C atoms Alkoxy, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 C atoms, or an alkoxycarbonyl group having 2 to 10 C atoms, or 7 to 10 An aryloxycarbonyl group of a C atom, a
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may form a single or multiple ring to each other and/or a ring to which the group is bonded Aliphatic or aromatic ring system.
  • One or more of the hydrogen atoms of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 or R 8 may be optionally substituted by a deuterium atom.
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II), and the others are independently selected.
  • the moieties may form a polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • One or more hydrogen atoms of the Ar 1 , Ar 2 , Ar 3 or Ar 4 may be further optionally substituted with a deuterium atom.
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II) And the other each independently selected from: a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms; One or more of the groups may form a polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • One or more hydrogen atoms of the Ar 1 , Ar 2 , Ar 3 or Ar 4 may be further optionally substituted with a deuterium atom.
  • Ar 1 , Ar 2 , Ar 3 or Ar 4 are the same or different from each other; at least one of the Ar 1 , Ar 2 , Ar 3 or Ar 4 is a group represented by the formula (II) And the other 4 are each independently selected from: a substituted or unsubstituted aromatic or heteroaromatic ring system having 10 to 25 ring atoms, or an aryloxy or heteroaryloxy group having 10 to 25 ring atoms.
  • One or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded.
  • One or more hydrogen atoms of the Ar 1 , Ar 2 , Ar 3 or Ar 4 may be further optionally substituted with a deuterium atom.
  • the aromatic ring system in the substituted or unsubstituted aryl group has from 5 to 15 carbon atoms in the parent core structure (ring system); in one embodiment, a substituted or unsubstituted aryl or hetero group
  • the aromatic ring system in the aryl group contains 5 to 10 carbon atoms in the parent core structure (ring system).
  • the total number of carbon atoms and heteroatoms of the parent core structure of the heteroaromatic ring system in the substituted or unsubstituted heteroaryl group is at least 4.
  • the heteronuclear structure (ring system) of the heteroaromatic ring system in the substituted or unsubstituted heteroaryl group contains 2 to 15 carbon atoms, and at least one hetero atom; in one embodiment, the substitution or The heteronuclear structure (ring system) of the heteroaromatic ring system in the unsubstituted heteroaryl group contains 2 to 10 carbon atoms, and at least one hetero atom.
  • the hetero atom may be Si, N, P, O, S and/or Ge; in one embodiment, the hetero atom is selected from the group consisting of Si, N, P, O and/or S; in one embodiment, the hetero atom Selected from N, O or S.
  • the above aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • the heteroaromatic ring or heteroaromatic group described above refers to a hydrocarbon group (containing a hetero atom) containing at least one heteroaromatic ring, and includes a monocyclic group and a polycyclic ring system.
  • These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • the aromatic or heteroaromatic ring system includes not only an aromatic or heteroaromatic system, but also a plurality of aryl or heteroaryl groups may be interrupted by short non-aromatic units ( ⁇ 10% of non-H atoms). Preferably, less than 5% of a non-H atom, such as a C, N or O atom). Therefore, a system such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine or diaryl ether is also considered to be an aromatic ring system.
  • the aromatic group is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, spiro and their derivatives.
  • the heteroaromatic group is selected from the group consisting of furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, and evil.
  • R 9 , R 10 , R 11 , R 12 or R 13 are the same or different from each other, and each of R 9 , R 10 , R 11 , R 12 , R 13 is independently selected from: H, or a linear alkyl group having 1 to 10 C atoms, or an alkoxy group having 1 to 10 C atoms, or a thioalkoxy group having 1 to 10 C atoms, or having 3 to 10 C atoms a branched or cyclic alkyl group, or an alkoxy group having 3 to 10 C atoms, or a thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted silyl group, or having a substituted keto group of 1 to 10 C atoms, or an alkoxycarbonyl group of 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group (-CN), a carbamoyl group
  • Ar 1 -Ar 4 may further optionally have the following structure:
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 respectively represent CR 3 or N;
  • R 3 , R 4 , R 5 are H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkane having 1 to 20 C atoms
  • Ar 1 -Ar 4 may be further selected from the following structures, wherein H on the ring may be optionally substituted:
  • an aromatic amine derivative is selected from the group consisting of the structure of formula (III):
  • Ar 7 , Ar 8 , Ar 9 , or Ar 10 are the same or different from each other, and each of Ar 7 , Ar 8 , Ar 9 , or Ar 10 is independently selected from: H, or has 1 to 20 a linear alkyl group of a C atom, or an alkoxy group having 1 to 20 C atoms, or a thioalkoxy group having 1 to 20 C atoms, or a branch or ring having 3 to 20 C atoms An alkyl group, or an alkoxy group having 3 to 20 C atoms, or a thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted silyl group, or having 1 to 20 a substituted keto group of a C atom, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C (
  • Ar 7 , Ar 8 , Ar 9 , or Ar 10 are the same or different from each other, and each of Ar 7 , Ar 8 , Ar 9 , or Ar 10 is independently selected from: H, or has 1 to 10 a linear alkyl group of a C atom, or an alkoxy group having 1 to 10 C atoms, or a thioalkoxy group having 1 to 10 C atoms, or a branch or ring having 3 to 10 C atoms An alkyl group, or an alkoxy group having 3 to 10 C atoms, or a thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted silyl group, or having 1 to 20 a substituted keto group of a C atom, or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group (-CN), a carbamoyl group (-C (
  • Ar 7 , Ar 8 , Ar 9 , or Ar 10 are the same or different from each other, and each of Ar 7 , Ar 8 , Ar 9 , or Ar 10 is independently selected from the group consisting of: H, D, methyl, Ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, methylbutyl, n-pentyl, sec-pentyl, cyclopentyl Base, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, ethylhexyl, trifluoromethyl, pentafluoroethyl, trifluoroethyl, vinyl, propenyl, butyl Alkenyl, pentenyl, pen
  • Y is CR 31 or N, but no two adjacent Ys are N at the same time;
  • R 31 is H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkoxy group having 1 to 20 C atoms, or having 3 a branched or cyclic alkyl group of up to 20 C atoms, or an alkoxy group having 3 to 20 C atoms, or a thioalkoxy group having 3 to 20 C atoms, or substituted or unsubstituted a silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, an amino group Formyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF 3 , Cl, Br, F, crosslink
  • R 31 is H, or a linear alkyl group having 1 to 10 C atoms, or an alkoxy group having 1 to 10 C atoms, or a thioalkane having 1 to 10 C atoms.
  • Ar 7 , Ar 8 , Ar 9 , or Ar 10 are each independently selected from the structures shown below:
  • a broken line indicates a single bond in which the group is bonded to the N atom of the aromatic amine.
  • the Ar 7 , Ar 8 , Ar 9 , or Ar 10 are each independently selected from the group consisting of: H, D, methyl, isopropyl, isobutyl, sec-butyl, tert-butyl, tri Methylsilane, cyclopentyl, cyclohexyl, phenyl or a phenyl group in which five hydrogen atoms are replaced by a halogen atom.
  • Ar 11, Ar 12 may be the same or different and the Ar 11, Ar 12 are each independently selected from: H, a substituted 5 to 40 ring atoms, unsubstituted aromatic or heteroaromatic ring system having 5 or An aryloxy or heteroaryloxy group to 40 ring atoms, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic group with each other and/or a ring bonded to the group Ring system.
  • One or more of the various groups described above may be further substituted with D.
  • Ar 11 and Ar 12 may be the same or different, and each of Ar 11 and Ar 12 is independently selected from: H, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 20 ring atoms. a ring system, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, wherein one or more groups may form a single or multiple ring to each other and/or a ring to which the group is bonded Aliphatic or aromatic ring system. One or more of the various groups described above may be further substituted with D.
  • Ar 11 and Ar 12 may be the same or different, and each of Ar 11 and Ar 12 is independently selected from: H, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 15 ring atoms. a ring system, or an aryloxy or heteroaryloxy group having 5 to 15 ring atoms, wherein one or more groups may form a single or multiple ring to each other and/or a ring to which the group is bonded Aliphatic or aromatic ring system. One or more of the various groups described above may be further substituted with D.
  • Z is CR 34 or N, but no two adjacent Zs are N at the same time;
  • R 32 , R 33 or R 34 are each independently selected from: H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or having 1 to 20 C a thioalkoxy group of an atom, or a branched or cyclic alkyl group having 3 to 20 C atoms, or an alkoxy group having 3 to 20 C atoms, or a thio group having 3 to 20 C atoms
  • An alkoxy group either a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or having 7 to 20 C
  • P is a saturated cycloalkane or heterocycloalkane having 3 to 10 ring atoms; a broken line indicates a single bond in which the group is bonded to the N atom of the aromatic amine.
  • P is a saturated cycloalkane or heterocycloalkane having 3 to 10 ring atoms, preferably a saturated cycloalkane or heterocycloalkane of 3 to 8 C atoms, more preferably a saturated cycloalkane or a heterocycle of 5 to 6 C atoms.
  • the dotted line indicates a single bond in which the group is bonded to the N atom of the aromatic amine.
  • the Ar 11 or Ar 12 are each independently selected from the structures shown below:
  • R 14 and R 15 may be the same or different, and R 14 or R 15 are each independently selected from: H, or a linear alkyl group having 1 to 10 C atoms, or 1 to 10 C.
  • R 14 and R 15 may be the same or different, and each of R 14 or R 15 is independently selected from a linear or branched alkane or a cycloalkane of 3 to 6 C atoms.
  • R 14 and R 15 may be the same or different, and R 14 or R 15 are each independently selected from a linear or branched alkane or a cycloalkane of 3-5 C atoms.
  • R 14 and R 15 may be the same or different, and R 14 or R 15 are each independently selected from a linear or branched alkane or a cycloalkane of 3-4 C atoms.
  • R 14 and R 15 may be the same or different, and R 14 or R 15 are each independently selected from: an aromatic or heteroaromatic group having 5 to 20 ring atoms.
  • R 14 and R 15 may be the same or different, and each of R 14 or R 15 is independently selected from: an aromatic or heteroaromatic group having 5 to 12 ring atoms.
  • R 14 and R 15 may be the same or different, and R 14 or R 15 are each independently selected from the group consisting of: an aromatic or heteroaromatic group having 5 to 12 ring atoms and at least one D. atom.
  • R 14 and R 15 are the same or different, and R 14 and R 15 are each independently selected from the group consisting of: H, D, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, Butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, N-octyl, cyclooctyl, ethylhexyl, trifluoromethyl, pentafluoroethyl, trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, Cyclohexenyl, heptenyl,
  • W is CR 35 or N, but no two adjacent Ws are N at the same time;
  • R 35 may be H, or a linear alkyl group having 1 to 20 C atoms, or an alkoxy group having 1 to 20 C atoms, or a thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group of 3 to 20 C atoms, or an alkoxy group having 3 to 20 C atoms, or a thioalkoxy group having 3 to 20 C atoms, or a substituted or unsubstituted a silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, Carboyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF 3 , Cl, Br, F, crosslinkable group
  • R 35 may be H, or a linear alkyl group having 1 to 10 C atoms, or an alkoxy group having 1 to 10 C atoms, or a thio group having 1 to 10 C atoms.
  • R 14 and R 15 are each independently selected from the group consisting of: H, D, isopropyl, isobutyl, tert-butyl, tetramethylsilane or substituted or unsubstituted aryl having the following structure Or heteroaryl:
  • R 14 and R 15 are the same or different, and each of R 14 and R 15 is independently selected from the group consisting of: H, D, isopropyl, isobutyl, tert-butyl, tetramethylsilane. , benzene, biphenyl, benzene containing at least one D atom or biphenyl having at least one D atom.
  • the R 14 and R 15 are the same and are selected from the group consisting of H, D, isopropyl, isobutyl, tert-butyl, tetramethylsilane, benzene, biphenyl, and at least one D atom. Benzene or biphenyl containing at least one D atom.
  • R 14 and R 15 are each selected from H. In one embodiment, R 14 and R 15 are both selected from D. In one embodiment, R 14 and R 15 are both selected from isopropyl. In one embodiment, R 14 and R 15 are each selected from the group consisting of isobutyl groups. In one embodiment, R 14 and R 15 are each selected from the group consisting of t-butyl groups. In one embodiment, R 14 and R 15 are each selected from the group consisting of tetramethylsilane. In one embodiment, R 14 and R 15 are each selected from the group consisting of benzene. In one embodiment, R 14 and R 15 are each selected from the group consisting of diphenyl. In one embodiment, R 14 and R 15 are each selected from benzene or diphenyl having at least one D atom.
  • the above compound is at least partially deuterated. In one embodiment, 10% of the H is deuterated; in one embodiment, 20% of the H is deuterated; in one embodiment, 30% of the H is deuterated; in one embodiment 40% H was replaced.
  • Ar 7 , Ar 8 , Ar 9 , or Ar 10 are the same as each other and are selected from the group consisting of methyl, phenyl or isopropyl;
  • Ar 11 and Ar 12 are the same as each other and are selected from the substituents shown below:
  • the R 14 and R 15 are a hydrogen atom or an isopropyl group or an isobutyl group or a tert-butyl group.
  • a specific example of an aromatic amine derivative according to the present invention is as follows, but is not limited thereto:
  • active materials comprise at least one leaving group, for example, bromine, iodine, boric acid or a boronic ester.
  • Suitable reactions to form C-C linkages are well known to those skilled in the art and are described in the literature.
  • Alternative coupling reactions are SUZUKI, STILLE and HECK coupling reactions.
  • a high polymer comprising at least one repeating unit selected from the above aromatic amine derivatives.
  • the high polymer is a non-conjugated high polymer wherein the aromatic amine derivative is attached to a side chain.
  • the high polymer is a conjugated high polymer.
  • a composition comprising the above aromatic amine derivative or the above-mentioned high polymer, and at least one organic solvent.
  • a mixture comprising the above aromatic amine derivative or the above high polymer, and at least one organic functional material selected from the group consisting of: a hole (also called a hole) injection or transport material (HIM/HTM), Hole blocking material (HBM), electron injecting or transporting material (EIM/ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescence) Luminous body), thermally excited delayed fluorescent material (TADF material) and organic dye.
  • a hole also called a hole injection or transport material
  • HBM Hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM electron blocking material
  • organic matrix material Host
  • singlet illuminant fluorescent illuminant
  • triplet illuminant phosphorescence
  • Luminous body thermally excited delayed fluorescent material
  • TADF material thermally excited delayed fluorescent material
  • the mixture comprises the above aromatic amine derivative or the above high polymer, and a fluorescent host material (or singlet matrix material).
  • the above aromatic amine derivative or the above high polymer may be used as a guest, and the weight percentage thereof is ⁇ 15% by weight;
  • the above aromatic amine derivative or the above-mentioned high polymer is ⁇ 12% by weight
  • the above aromatic amine derivative or the above polymer has a weight percentage of ⁇ 9 wt%
  • the above aromatic amine derivative or the above-mentioned high polymer has a weight percentage of ⁇ 7 wt%.
  • the mixture comprises the above aromatic amine derivative or the above-described high polymer, another fluorescent illuminant (or singlet illuminant) and a fluorescent host material.
  • another fluorescent illuminant or singlet illuminant
  • a fluorescent host material e.g., a fluorescent material that is used as an auxiliary luminescent material, and its weight ratio to another fluorescent illuminant is from 1:2 to 2:1.
  • the mixture comprises one of the above aromatic amine derivatives or the above-described polymers, and a TADF material.
  • the mixture comprises an aromatic amine derivative as described above or a high polymer as described above, and an HTM material.
  • HTM singlet matrix materials
  • singlet emitters singlet emitters
  • Suitable organic HIM/HTM materials may optionally comprise compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, thiophene such as dithienothiophene and thiophene, pyrrole, aniline , carbazole, azide and azepine and their derivatives.
  • suitable HIMs also include self-assembling monomers such as compounds containing phosphonic acid and sliane derivatives; metal complexes and crosslinking compounds and the like.
  • An electron blocking layer is used to block electrons from adjacent functional layers, particularly the luminescent layer.
  • the electron blocking material (EBM) of the electron blocking layer (EBL) requires a higher LUMO than an adjacent functional layer such as a light emitting layer.
  • the HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant, while the EBM has a hole transport function.
  • HIM/HTM materials that typically have high LUMO levels can be used as EBMs.
  • cyclic aromatic amine-derived compounds useful as HIM, HTM or EBM include, but are not limited to, the following general structures:
  • Each of Ar 1 to Ar 9 may be independently selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; Heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, evil Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, acesulfazine, oxadiazine, hydrazine
  • Ar 1 to Ar 9 may be independently selected from the group consisting of:
  • n is an integer from 1 to 20; X 1 to X 8 are CH or N; and Ar 1 is as defined above.
  • metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:
  • M is a metal having an atomic weight greater than 40
  • (Y 1 -Y 2 ) is a two-dentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to The maximum coordination number of this metal; m+n is the maximum coordination number of this metal.
  • (Y 1 -Y 2 ) is a 2-phenylpyridine derivative.
  • (Y 1 -Y 2 ) is a carbene ligand.
  • M is selected from Ir, Pt, Os, and Zn.
  • the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).
  • the example of the singlet host material is not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.
  • Examples of the organic compound used as the singlet host material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene, An aromatic heterocyclic compound such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridine Anthraquinone, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrim
  • the singlet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar 1 is an aryl group Or a heteroaryl group, which has the same meaning as Ar 1 defined in the above HTM;
  • n is an integer from 0 to 20;
  • X 1 -X 8 is selected from CH or N;
  • X 9 and X 10 are selected from CR 1 R 2 Or NR 1 .
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • the singlet emitter may be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and arylamine.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1 hereby incorporated herein in its entirety This article serves as a reference.
  • Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, preferably ⁇ Est ⁇ 0.3 eV, and secondly ⁇ Est ⁇ 0.2 eV, preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, In another preferred embodiment, TADF has better fluorescence quantum efficiency.
  • TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064( A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett ., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials are listed in the table below:
  • a composition comprising the above aromatic amine derivative or a high polymer thereof or a mixture thereof, and an organic solvent.
  • the deuterated aromatic amine derivative is used as a singlet emitter material.
  • composition comprising a host material and the above aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • composition comprising at least two host materials and the above aromatic amine derivatives or polymers thereof or mixtures thereof.
  • composition comprising a host material, a thermally activated delayed fluorescent luminescent material and the above aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • composition comprising a hole transporting material (HTM) and the above aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • HTM hole transporting material
  • a composition comprising a hole transporting material (HTM) comprising a crosslinkable group and the above aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • HTM hole transporting material
  • the above composition is a solution.
  • the above composition is a suspension.
  • the composition comprises 0.01% by weight to 20% by weight of the above aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • the composition comprises 0.1% by weight to 15% by weight of the above aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • the composition comprises 0.2% by weight to 10% by weight of the above aromatic amine derivative or a high polymer thereof or a mixture thereof;
  • the composition comprises from 0.25 wt% to 5 wt% of the above aromatic amine derivative or a high polymer thereof or a mixture thereof.
  • a composition the solvent used in the composition is selected from the group consisting of: an aromatic or heteroaromatic, an ester, an aromatic ketone or an aromatic ether, an aliphatic ketone or an aliphatic ether, an alicyclic or An olefinic compound, or an inorganic ester compound such as a boronic acid ester or a phosphate ester, or a mixture of two or more solvents.
  • composition comprising at least 50% by weight of an aromatic or heteroaromatic solvent
  • composition comprising at least 80% by weight of an aromatic or heteroaromatic solvent
  • composition comprising at least 90% by weight of an aromatic or heteroaromatic solvent.
  • examples based on aromatic or heteroaromatic solvents are, but are not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diiso Propylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene , m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecane Benzobenzene, 1-methylnaphthalene, 1,2,4-trich
  • suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, glycols or polyols.
  • the alcohol represents a suitable class of solvent.
  • Preferred alcohols include alkylcyclohexanols, especially methylated aliphatic alcohols, naphthols and the like.
  • the solvent may be a cycloalkane such as decalin.
  • the solvent may be used singly or as a mixture of two or more organic solvents.
  • the above composition comprises one of the above aromatic amine derivatives or a high polymer thereof, and at least one organic solvent, and may further comprise another organic solvent, and another organic solvent is exemplified.
  • organic solvent Including but not limited to: methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, and Xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, de
  • the organic solvent in the above composition is a solvent having a Hansen solubility parameter in the following range:
  • ⁇ d (dispersion force) is in the range of 17.0 to 23.2 MPa 1/2 , especially in the range of 18.5 to 21.0 MPa 1/2 ;
  • ⁇ p polar forces in the range of 0.2 ⁇ 12.5MPa 1/2, especially in the 2.0 ⁇ 6.0MPa 1/2;
  • the boiling point parameter should be considered when selecting the organic solvent in the above composition.
  • the boiling point of the organic solvent is ⁇ 1501 C; in one embodiment, the boiling point of the organic solvent is ⁇ 180 ° C; in one embodiment, the boiling point of the organic solvent is ⁇ 200 ° C; In one embodiment, the organic solvent has a boiling point of ⁇ 250 ° C; in one embodiment, the organic solvent has a boiling point of ⁇ 275 ° C; in one embodiment, the organic solvent has a boiling point of ⁇ 300 ° C. .
  • the boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead.
  • the organic solvent can be evaporated from the solvent system to form a film comprising the functional material.
  • a composition the viscosity of the selected solvent, has a surface tension as follows:
  • the surface tension parameter should be considered when selecting the organic solvent in the above composition. Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method. For example, for inkjet printing, in one embodiment, the surface tension of the organic solvent at 25 ° C is in the range of about 19 dyne / cm to 50 dyne / cm; the surface tension of the organic solvent at 25 ° C is about 22 dyne The range of /cm to 35dyne/cm; the surface tension of the organic solvent at 25 ° C is in the range of about 25 dyne / cm to 33 dyne / cm.
  • the surface tension of the ink at 25 ° C is in the range of from about 19 dyne / cm to 50 dyne / cm; in one embodiment, the surface tension of the ink at 25 ° C is in the range of from about 22 dyne / cm to 35 dyne / cm; In one embodiment, the ink has a surface tension at 25 ° C ranging from about 25 dyne/cm to 33 dyne/cm.
  • the viscosity parameter of the ink should be considered when selecting the organic solvent in the composition.
  • the viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional material in the ink.
  • the organic solvent has a viscosity of less than 100 cps; in one embodiment, the organic solvent has a viscosity of less than 50 cps; in one embodiment, the organic solvent has a viscosity of 1.5 to 20cps.
  • the viscosity herein refers to the viscosity at ambient temperature at the time of printing, and is usually 15 to 30 ° C, preferably 18 to 28 ° C, more preferably 20 to 25 ° C, and most preferably 23 to 25 ° C. Compositions so formulated will be particularly suitable for ink jet printing.
  • a composition has a viscosity at 25 ° C in the range of from about 1 cps to about 100 cps; in one embodiment, a composition having a viscosity at 25 ° C in the range of from about 1 cps to about 50 cps; In the embodiment, one The composition has a viscosity at 25 ° C in the range of about 1.5 cps to 20 cps.
  • the ink obtained by the organic solvent satisfying the above boiling point and surface tension parameters and viscosity parameters can form a functional material film having uniform thickness and composition properties.
  • the organic electronic device can be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic spintronic device.
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • OLED organic light emitting field effect transistor
  • the above aromatic amine derivative or a high polymer or mixture thereof is formed into a functional layer on a substrate by evaporation, or formed by co-evaporation on at least one other organic functional material on a substrate.
  • a functional layer, or coating the above composition on a substrate by printing or coating to form a functional layer wherein the printing or coating method can be selected from, but not limited to, inkjet printing, printing ( Nozzle Printing), Typography, Screen Printing, Dip Coating, Spin Coating, Blade Coating, Roller Printing, Twist Roll Printing, Lithography, Flexo Printing, Rotary Printing, Spraying, Brushing or Pad Printing, Slits Type extrusion coating, etc.
  • the above composition is used as a printing ink for the preparation of an organic electronic device.
  • the above-described organic electronic device is prepared by a printing or coating preparation method.
  • suitable printing or coating techniques can be inkjet printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, lithography, flexographic printing, and rotary printing. , spraying, brushing or pad printing, slit type extrusion coating, etc.
  • Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention.
  • the solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the functional layer formed by the above described preparation method has a thickness of from 5 nm to 1000 nm.
  • An organic electronic device comprising at least one of the above aromatic amine derivatives or a high polymer thereof, or at least a functional layer prepared by using the above composition.
  • an organic electronic device includes: a cathode, an anode, and a functional layer between the cathode and the anode, wherein the functional layer contains at least one aromatic amine derivative as described above or a high thereof Polymer or a mixture of the above or a combination of the above.
  • the organic electronic device described above is an electroluminescent device, particularly an OLED (shown in FIG. 1), including a substrate 101, an anode 102, at least one luminescent layer 104, and a cathode 106. .
  • the substrate 101 can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-n
  • the anode 102 can comprise a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art.
  • Anode material can It is deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • Cathode 106 can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the OLED may further include other functional layers such as a hole injection layer (HIL) or a hole transport layer (HTL) 103, an electron blocking layer (EBL), an electron injection layer (EIL) or an electron transport layer (ETL) 105, and a hole. Barrier layer (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL Barrier layer
  • the light-emitting layer 104 in the light-emitting device is vacuum-deposited, and the evaporation source thereof contains the above aromatic amine derivative or a high polymer thereof or a combination thereof or a mixture thereof.
  • the luminescent layer 104 in the light emitting device is prepared by printing the above aromatic amine derivative of the present invention or a high polymer thereof or a composition thereof or a mixture thereof.
  • the electroluminescent device has an emission wavelength between 300 and 1000 nm; in one embodiment, the electroluminescent device has an emission wavelength between 350 and 900 nm; in one embodiment, the electroluminescent device The illuminating wavelength is between 400 and 800 nm.
  • organic electronic devices are used in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.
  • the electronic device of the above organic electronic device includes, but is not limited to, a display device, a lighting device, a light source, a sensor, and the like.
  • the present invention does not indicate a reagent or instrument of a specific source, and is a conventional reagent or instrument purchased from the market.
  • 1,6-dibromoindole (3.6 g, 10 mmol), N-(2,7-diphenylnaphthalen-1-yl)-dibenzofuran- 4-amine (9.2 g, 20 mmol), Pd(dba) 2 (345 mg, 0.6 mmol), NaOtBu (5.76 g, 60 mmol), (tBu) 3 P (360 mg, 1.8 mmol) and 100 mL of anhydrous toluene, stirred at 100 ° C overnight. After completion of the reaction, the precipitated solid was filtered, washed with toluene and methanol to give pale-yellow solid powder (8.2 g, 73%).
  • 1,6-dibromoindole 5.04 g, 14 mmol
  • N-(2,7-dimethylnaphthalen-1-yl)-4a 9a-di Methyl-9-phenyl-1,2,3,4,4a,9a-hexahydro-oxazol-6-amine
  • Pd(dba) 2 480 mg, 0.84 mmol
  • NaOtBu 8.06 g, 84 mmol
  • (tBu) 3 P 505 mg, 2.5 mmol
  • the precipitated solid was filtered, washed with toluene and methanol to give pale yellow solid powder (10.1 g, 66%).
  • HIL a triarylamine derivative
  • HTL a triarylamine derivative
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • HIL 50 nm
  • HTL 35 nm
  • EML 25 nm
  • ETL 28 nm
  • cathode LiQ / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency. It has been found that the color coordinates of the blue light device prepared by using Compound 1 - Compound 10 as the EML layer illuminant are better than that of Comparative Compound 1, for example, the color coordinates of the device prepared by Compound 5 are (0.149, 0.084); The luminous efficiency of the blue light device prepared by the compound 10 as the EML layer illuminant is in the range of 6-8 cd/A, which has more excellent luminous efficiency; in terms of device lifetime, the blue light device is prepared by using the compound 1 - compound 10 as the EML layer illuminant. The lifetime is better than that of Comparative Compound 1, for example, the device prepared by Compound 5 has a T95 position at 1000 nits for 1530 hours.

Abstract

本发明涉及一种如通式(I)所示的芳香胺衍生物：上述芳香胺衍生物，具有发光波长位于短波长的荧光发射，其发光光谱表现为具有窄的半峰宽，从而该类物质具有深蓝色的荧光发射，且具有高的发光效率。以此类芳香胺衍生物制备得到的有机电致发光元件具有深蓝的色坐标、高的发光效率、及长的器件寿命。

Description

芳香胺衍生物及其制备方法和用途 技术领域
本发明涉及有机电致发光技术领域，特别是涉及一种芳香胺衍生物，混合物及组合物，及其在有机电致发光领域的应用。
本申请要求于2016年11月23日提交中国专利局、申请号为201611048273.9、发明名称为“芳香胺衍生物及其在有机电子器件的应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
背景技术
由于有机半导体材料在合成上具有多样性、制造成本相对较低和优良的光学与电学性能，有机发光二极管(OLED)在光电器件(例如平板显示器和照明)的应用方面具有很大的潜力。
有机电致发光现象是指利用有机物质将电能转化为光能的现象。利用有机电致发光现象的有机电致发光元件通常具有正极与负极以及在它们中间包含有机物层的结构。为了提高有机电致发光元件的效率与寿命，有机物层具有多层结构，每一层包含有不同的有机物质。具体的，可以包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层等。在这种有机电致发光元件中，在两个电极之间施加电压，则由正极向有机物层注入空穴，有负极向有机物曾注入电子，当注入的空穴与电子相遇时形成激子，该激子跃迁回基态时发出光。这种有机电致发光元件具有自发光、高亮度、高效率、低驱动电压、广视角、高对比度、高响应性等特性。
为了提高有有机电致发光元件的发光效率，各种基于荧光和磷光的发光材料体系已被开发出来，而无论是荧光材料还是磷光材料，优秀蓝光材料的开发都是一个巨大的挑战，总体而言，目前使用的蓝光荧光材料的有机发光二级管可靠性更高。尽管如此，目前大多数蓝光荧光材料的发射光谱过宽，色纯度较差，不利于高端显示，并且这类荧光材料的合成也较复杂，不利于大规模量产，同时这类蓝色荧光材料的OLED稳定性还需进一步提高。因此开发具有窄带发射光谱、稳定性好的蓝色荧光材料，一方面有利于得到更长寿命更高效率的蓝光器件，另一方面有利于色域的提高，进而改善显示效果。
现有技术的蓝光有机电致发光元件发光层采用主客体掺杂结构。作为现有的蓝光主体材料是基于蒽的稠环类衍生物，如专利CN1914293B、CN102448945B、US2015287928A1等所述，然而这些化合物存在发光效率和亮度不充分的问题，及器件寿命较差的问题。作为现有技术的发蓝光客体化合物，可采用的是芳基乙烯基胺类化合物(WO 04/013073,WO 04/016575,WO 04/018587)。然而，这些化合物的热稳定性差，易分解，导致器件的寿命差，是目前产业上最主要的缺点。此外，这些化合物的色纯度差，难以实现深蓝色的发光。另外，US 7233019、KR 2006-0006760等专利公开了利用芳基胺取代基的芘系化合物的有机电致发光元件，但是因为蓝光的色纯度低，很难实现深蓝发光，因此在体现天然颜色的全彩色显示器方面有问题。
因此，仍需进一步改进材料，特别是发光化合物，尤其是蓝色发光化合物。使蓝光发光材料能具有深蓝色发光，且它们是热稳定的，在有机电致发光元件中体现良好的效率和寿命，在器件的制造与操作中易于重复，且材料合成简单。
发明内容
一种如通式(I)所示的芳香胺衍生物：
Figure PCTCN2017112703-appb-000001
其中，
R1、R2、R3、R4、R5、R6、R7或R8彼此相同或不同，所述R1、R2、R3、R4、R5、R6、R7或R8各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
R1、R2、R3、R4、R5、R6、R7或R8中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
所述R1、R2、R3、R4、R5、R6、R7或R8中的一个或多个氢原子任选被氘原子取代。
Ar1、Ar2、Ar3或Ar4彼此相同或不同；所述Ar1、Ar2、Ar3或Ar4中至少有一个是通式(II)所示的基团，其他各自独立地选自：具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
其中Ar1、Ar2、Ar3或Ar4中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系；
所述Ar1、Ar2、Ar3或Ar4中的一个或多个氢原子可以进一步任选被氘原子取代；
通式(II)的结构为：
Figure PCTCN2017112703-appb-000002
其中，
R9、R10、R11、R12或R13彼此相同或不同，所述R9、R10、R11、R12、R13各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至 20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤代甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
所述R9、R10、R11、R12或R13中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
Ar5、Ar6相同或不同，所述Ar5或Ar6各自独立地选自：H、或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
Ar5、Ar6中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系；
所述R9、R10、R11、R12、R13、Ar5、或Ar6中的一个或多个氢原子可以进一步任选被氘原子取代；
虚线表示与通式(I)相连接的单键。
一种高聚物，包含至少一个重复单元，所述重复单元选自上述芳香胺衍生物。
一种组合物，包括上述的芳香胺衍生物或上述的高聚物，以及至少一种有机溶剂。
一种混合物，包括上述的芳香胺衍生物或上述的高聚物、以及至少一种有机功能材料，所述有机功能材料选自：空穴(也称电洞)注入或传输材料(HIM/HTM)，空穴阻挡材料(HBM)，电子注入或传输材料(EIM/ETM)，电子阻挡材料(EBM)，有机基质材料(Host)，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)、热激发延迟荧光材料(TADF材料)及有机染料。
通式(I)所示的芳香胺衍生物或上述的高聚物或上述组合物或上述混合物在有机电子器件中的应用。
一种有机电致发光器件，包括：阴极、阳极以及有机层，，所述有机层上述的芳香胺衍生物或上述的高聚物或上述的组合物或上述的混合物所形成。
上述芳香胺衍生物，具有发光波长位于短波长的荧光发射，其发光光谱表现为具有窄的半峰宽，从而该类物质具有深蓝色的荧光发射，且具有高的发光效率。以此类芳香胺衍生物制备得到的有机电致发光元件具有深蓝的色坐标、高的发光效率、及长的器件寿命。
附图说明
图1是一实施例的电子器件的示意图。
具体实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的 实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
在本发明中，主体材料、基质材料、Host材料和Matrix材料具有相同的含义，可以互换。
在本发明中，金属有机络合物，金属有机配合物，有机金属配合物具有相同的含义，可以互换。
在本发明中，组合物、印刷油墨、油墨、和墨水具有相同的含义，可以互换。
本发明中，“H”和氢原子具有相同的含义，“D”和氘原子具有相同的含义。
在本发明中，“任选被取代”与“还可进一步被取代”具有相同的含义，可以互换，是指可以被取代，也可以不被取代，例如：Ar6中的一个或多个氢原子任选被氘原子取代是指Ar6中的一个或多个氢原子可以被氘原子取代，也可以不被氘原子取代。
一种如通式(I)所示的芳香胺衍生物：
Figure PCTCN2017112703-appb-000003
其中，
R1、R2、R3、R4、R5、R6、R7或R8彼此相同或不同，所述R1、R2、R3、R4、R5、R6、R7或R8各自独立地选自：H、，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
R1、R2、R3、R4、R5、R6、R7或R8中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
所述R1、R2、R3、R4、R5、R6、R7或R8中的一个或多个氢原子可以进一步任选被氘原子取代；
在一实施例中，R1、R2、R3、R4、R5、R6、R7或R8彼此相同或不同；所述R1、R2、R3、R4、R5、R6、R7或R8各自独立地选自：H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰 基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团；
R1、R2、R3、R4、R5、R6、R7或R8中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。所述R1、R2、R3、R4、R5、R6、R7或R8中的一个或多个氢原子任选被氘原子取代。
Ar1、Ar2、Ar3或Ar4彼此相同或不同；所述Ar1、Ar2、Ar3或Ar4中至少有一个是通式(II)所示的基团，其他各自独立地选自：具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；其中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系。所述Ar1、Ar2、Ar3或Ar4中的一个或多个氢原子可以进一步任选被氘原子取代。
在一实施例中，Ar1、Ar2、Ar3或Ar4彼此相同或不同；所述Ar1、Ar2、Ar3或Ar4中至少有一个是通式(II)所示的基团，其他各自独立地选自：具有5至30个环原子的取代或未取代的芳族或杂芳族环系，或具有5至30个环原子的芳氧基或杂芳氧基基团；其中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系。所述Ar1、Ar2、Ar3或Ar4中的一个或多个氢原子可以进一步任选被氘原子取代。
在一实施例中，Ar1、Ar2、Ar3或Ar4彼此相同或不同；所述Ar1、Ar2、Ar3或Ar4中至少有一个是通式(II)所示的基团，其他4各自独立地选自：具有10至25个环原子的取代或未取代的芳族或杂芳族环系，或具有10至25个环原子的芳氧基或杂芳氧基基团；其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。所述Ar1、Ar2、Ar3或Ar4中的一个或多个氢原子可以进一步任选被氘原子取代。
在一实施例中，取代或未取代的芳基中的芳香环系的母核结构(环系)中包含5～15个碳原子；在一实施例中，取代或未取代的芳基或杂芳基中的芳香环系的母核结构(环系)中包含5～10个碳原子。
取代或未取代杂芳基中的杂芳香环系的母核结构的碳原子和杂原子的总数至少为4。在一实施例中，取代或未取代杂芳基中的杂芳香环系的母核结构(环系)中包含2～15个碳原子，和至少一个杂原子；在一实施例中，取代或未取代杂芳基中的杂芳香环系的母核结构(环系)中包含2～10个碳原子，和至少一个杂原子。其中，杂原子可以是Si、N、P、O、S和/或Ge；在一实施例中，杂原子选自Si、N、P、O和/或S；在一实施例中，杂原子选自N、O或S。
以上所述的芳香环系或芳族基团指至少包含一个芳环的烃基，包括单环基团和多环的环系统。以上所述的杂芳香环系或杂芳族基团指包含至少一个杂芳环的烃基(含有杂原子)，包括单环基团和多环的环系统。这些多环的环可以具有两个或多个环，其中两个碳原子被两个相邻的环共用，即稠环。多环的这些环种，至少一个是芳族的或杂芳族的。另外，芳香族或杂芳香族环系不仅包括芳香基或杂芳香基的体系，而且，其中多个芳基或杂芳基也可以被短的非芳族单元间断(<10％的非H原子，优选小于5％的非H原子,比如C、N或O原子)。因此，比如9,9'-螺二芴，9,9-二芳基芴，三芳胺，二芳基醚等体系，同样认为是芳香族环系。
在一实施例中，芳族基团选自：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、螺芴及其衍生物。
在一实施例中，杂芳族基团选自：呋喃、苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、二苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、喹唑啉、喹唑啉酮、及其衍生物。
所述通式(II)的结构为：
Figure PCTCN2017112703-appb-000004
其中，
R9、R10、R11、R12或R13彼此相同或不同，所述R9、R10、R11、R12、R13各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中，R9、R10、R11、R12或R13彼此相同或不同，所述R9、R10、R11、R12、R13各自独立地选自：H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
Ar5、Ar6相同或不同，所述Ar5或Ar6各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步任选被D所取代。
在一实施例中，Ar5、Ar6相同或不同，所述Ar5或Ar6各自独立地选自：H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个 C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步任选被D所取代。
虚线表示与通式(I)相连接的单键。
在一实施例中，Ar1-Ar4还可进一步任选如下结构：
Figure PCTCN2017112703-appb-000005
其中，
A1、A2、A3、A4、A5、A6、A7、A8分别独立表示CR3或N；
Y1选自CR4R5、SiR4R5、NR3、C(＝O)、S或O；
R3、R4、R5是H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团R3，R4，R5可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环。
在一实施例中，Ar1-Ar4还可进一步选于如下结构，其中环上的H可以被任意取代：
Figure PCTCN2017112703-appb-000006
在一个实施例中，一种芳香胺衍生物，选自具有通式(III)所示的结构：
Figure PCTCN2017112703-appb-000007
其中，
在一实施例中，Ar7、Ar8、Ar9、或Ar10彼此相同或不同，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中，Ar7、Ar8、Ar9、或Ar10彼此相同或不同，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自：H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中，Ar7、Ar8、Ar9、或Ar10彼此相同或不同，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自：H、D、甲基，乙基，正丙基，异丙基，环丙基，正丁基，异丁基，仲丁基，叔丁基，环丁基，甲基丁基，正戊基，仲戊基，环戊基，正己基，环己基，正庚基，环庚基，正辛基，环辛基，乙基己基，三氟甲基，五氟乙基，三氟乙基，乙烯基，丙烯基，丁烯基，戊烯基，环戊烯基，己烯基，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、辛炔基、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，叔丁氧基或甲基丁氧基、三甲基硅烷，或具有以下母核结构的取代或未取代芳基或杂芳基：
Figure PCTCN2017112703-appb-000008
Figure PCTCN2017112703-appb-000009
Y是CR31或N，但没有两个相邻的Y同时为N；
R31是H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤代甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；R31中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；R31中的一个或多个H任选进一步被D所取代；虚线表示所述基团与芳香胺的N原子连接的单键。
在一实施例中，R31是H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中所述Ar7、Ar8、Ar9、或Ar10各自独立地选自以下所示的结构：
Figure PCTCN2017112703-appb-000010
Figure PCTCN2017112703-appb-000011
上述结构中，虚线表示所述基团与芳香胺的N原子连接的单键。
在一实施例中，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自：H、D、甲基、异丙基、异丁基、仲丁基、叔丁基、三甲基硅烷、环戊基、环己基、苯基或5个氢原子被氘原子取代的苯基。
Ar11、Ar12可以相同或不同，所述Ar11、Ar12各自独立地选自：H，具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中，Ar11、Ar12可以相同或不同，所述Ar11、Ar12各自独立地选自：H，具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中，Ar11、Ar12可以相同或不同，所述Ar11、Ar12各自独立地选自：H，具有5至15个环原子的取代或未取代的芳族或杂芳族环系，或具有5至15个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
当所述Ar11或Ar12各自独立地选自以下所示的结构：
Figure PCTCN2017112703-appb-000012
Z是CR34或N，但没有两个相邻的Z同时为N；
R32、R33或R34各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；所述R32、R33或R34中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；所述R32、R33或R34中的一个或多个H任选进一步被D所取代；
P是具有3到10个环原子的饱和环烷烃或杂环烷烃；虚线表示所述基团与芳香胺的N原子连接的单键。
在一实施例中，R32、R33或R34各自独立地选自：H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基 (-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
P是具有3到10个环原子的饱和环烷烃或杂环烷烃，优选为3-8个C原子的饱和环烷烃或杂环烷烃，更优为5-6个C原子的饱和环烷烃或杂环烷烃。虚线表示所述基团与芳香胺的N原子连接的单键。
所述Ar11或Ar12为各自独立地选自以下所示的结构：
Figure PCTCN2017112703-appb-000013
Figure PCTCN2017112703-appb-000014
R14、R15可以相同或不同，R14或R15各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中，R14、R15可以相同或不同，R14或R15各自独立地选自：H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。
在一实施例中，上述R14、R15可以相同或不同，R14或R15各自独立地选自：3-6个C原子的直链或支链烷烃或环烷烃。
在一实施例中，上述R14、R15可以相同或不同，R14或R15各自独立地选自：3-5个C原子的直链或支链烷烃或环烷烃。
在一实施例中，上述R14、R15可以相同或不同，R14或R15各自独立地选自：3-4个C原子的直链或支链烷烃或环烷烃。
在一实施例中，上述R14、R15可以相同或不同，R14或R15各自独立地选自：具有5-20个环原子的芳族或杂芳族基团。
在一实施例中，上述R14、R15可以相同或不同，R14或R15各自独立地选自：具有5-12个环原子的芳族或杂芳族基团。
在一实施例中，上述R14、R15可以相同或不同，R14或R15各自独立地选自：具有5-12个环原子的芳族或杂芳族基团中还至少含有一个D原子。
在一实施例中，上述R14、R15相同或不同，R14、R15各自独立地选自：H、D、甲基，乙基，正丙基，异丙基，环丙基，正丁基，异丁基，仲丁基，叔丁基，环丁基，甲基丁基，正戊基，仲戊基，环戊基，正己基，环己基，正庚基，环庚基，正辛基，环辛基，乙基己基，三氟甲基，五氟乙基，三氟乙基，乙烯基，丙烯基，丁烯基，戊烯基，环戊烯基，己烯基，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、辛炔基、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，叔丁氧基或甲基丁氧基、三甲基硅烷，或具有以下结构的取代或未取代芳基或杂芳基：
Figure PCTCN2017112703-appb-000015
W是CR35或N，但没有两个相邻的W同时为N；
R35可以是H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；R35中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；所述R35中的一个或多个H还可进一步被D所取代；虚线表示 所述基团与其它基团连接的单键。
在一实施例中，R35可以是H，或者具有1至10个C原子的直链烷基、或者具有1至10个C原子的烷氧基、或者具有1至10个C原子的硫代烷氧基，或者具有3至10个C原子的支链或环状的烷基、或者具有3至10个C原子的烷氧基、或者具有3至10个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至10个C原子的取代的酮基，或具有2至10个C原子的烷氧基羰基，或具有7至10个C原子的芳氧基羰基，氰基(-CN)，氨基甲酰基(-C(＝O)NH2)，卤甲酰基(-C(＝O)-X其中X代表卤素原子),甲酰基(-C(＝O)-H)，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至20个环原子的取代或未取代的芳族或杂芳族环系，或具有5至20个环原子的芳氧基或杂芳氧基基团，其中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系。以上所述的各种基团中的一个或多个H还可进一步被D所取代。虚线表示所述基团与芳香胺的N原子连接的单键。
在一实施例中，所述R14、R15各自独立地选自：H、D、异丙基、异丁基、叔丁基、四甲基硅烷或具有以下结构的取代或未取代芳基或杂芳基：
Figure PCTCN2017112703-appb-000016
在一实施例中，所述R14和R15相同或不同，所述R14、R15各自独立地选自：H、D、异丙基、异丁基、叔丁基、四甲基硅烷、苯、二联苯、至少含有一个D原子的苯或至少含有一个D原子的二联苯。
在一实施例中，所述R14和R15相同，选自：H、D、异丙基、异丁基、叔丁基、四甲基硅烷、苯、二联苯、至少含有一个D原子的苯或至少含有一个D原子的二联苯。
在一实施例中，R14、R15都选自H。在一实施例中，R14、R15都选自D。在一实施例中，R14、R15都选自异丙基。在一实施例中，R14、R15都选自异丁基。在一实施例中，R14、R15都选自叔丁基。在一实施例中，R14、R15都选自四甲基硅烷。在一实施例中，R14、R15都选自苯。在一实施例中，R14、R15都选自二连苯。在一实施例中，R14、R15都选自至少含有一个D原子的苯或二连苯。
在一实施例中，上述化合物是至少部分被氘代。在一实施例中，10％的H被氘代；在一实施例中，20％的H被氘代；在一实施例中，30％的H被氘代；在一实施例中40％的H被氘代。
在一实施例中，以下通式(III)所示的结构中，
Figure PCTCN2017112703-appb-000017
Ar7、Ar8、Ar9、或Ar10彼此相同，选自：甲基、苯基或异丙基；
Ar11和Ar12彼此相同，选自以下所示的取代基：
Figure PCTCN2017112703-appb-000018
所述R14、R15为氢原子或异丙基或异丁基或叔丁基。
按照本发明的一种芳香胺衍生物，其具体的例子如下，但不仅限于此：
Figure PCTCN2017112703-appb-000019
Figure PCTCN2017112703-appb-000020
Figure PCTCN2017112703-appb-000021
Figure PCTCN2017112703-appb-000022
Figure PCTCN2017112703-appb-000023
Figure PCTCN2017112703-appb-000024
Figure PCTCN2017112703-appb-000025
Figure PCTCN2017112703-appb-000026
Figure PCTCN2017112703-appb-000027
Figure PCTCN2017112703-appb-000028
一种通式(I)-(III)的芳香胺衍生物的合成方法，其中使用含有活性基团的原料进行反应。这些活性原料包含至少一种离去基团，例如，溴，碘，硼酸或硼酸酯。形成C-C连接的适当的反应是本领域技术人员熟知的并描述于文献中，可以选择的偶联反应有SUZUKI，STILLE和HECK偶联反应。
一种高聚物，包含至少一个重复单元，所述重复单元选自上述芳香胺衍生物。在一实施例中，所述的高聚物是非共轭高聚物，其中所述芳香胺衍生物连接在侧链上。在实施例中，所述的高聚物是共轭高聚物。
一种组合物，包括上述芳香胺衍生物或上述的高聚物，以及至少一种有机溶剂。
一种混合物，包括上述芳香胺衍生物或上述高聚物、以及至少一种有机功能材料，所述有机功能材料选自：空穴(也称电洞)注入或传输材料(HIM/HTM)，空穴阻挡材料(HBM)，电子注入或传输材料(EIM/ETM)，电子阻挡材料(EBM)，有机基质材料(Host)，单重态发光体(荧光发光体)，三重态发光体(磷光发光体)、热激发延迟荧光材料(TADF材料)及有机染料。例如在WO2010135519A1,US20090134784A1和WO 2011110277A1中对各种有机功能材料有详细的描述，特此将此3专利文件中的全部内容并入本文作为参考。
在一实施例中，所述的混合物包含上述芳香胺衍生物或上述高聚物，和一种荧光主体材料(或单重态基质材料)。上述芳香胺衍生物或上述高聚物可以作为客体，其重量百分比≤15wt％；
在一实施例中，上述芳香胺衍生物或上述的高聚物的重量百分比≤12wt％；
在一实施例中，上述芳香胺衍生物或上述的高聚物的重量百分比≤9wt％；
在一实施例中，上述芳香胺衍生物或上述的高聚物的重量百分比≤8wt％；
在一实施例中，上述芳香胺衍生物或上述的高聚物的重量百分比≤7wt％。
在一个实施例中，所述的混合物包含上述芳香胺衍生物或上述的高聚物的、另一种荧光发光体(或单重态发光体)以及一种荧光主体材料。其中，上述芳香胺衍生物或上述的高聚 物的可以作为辅助发光材料，其与另一种荧光发光体的重量比为从1:2到2:1。
某些实施例中，所述的混合物包含一种上述芳香胺衍生物或上述的高聚物的，和TADF材料。
在另一实施例中，所述的混合物包含一种上述芳香胺衍生物或上述的高聚物，和HTM材料。
下面对HTM，单重态基质材料，单重态发光体和TADF材料作一些较详细的描述(但不限于此)。
1.HIM/HTM/EBM
合适的有机HIM/HTM材料可选包含有如下结构单元的化合物:酞菁、卟啉、胺、芳香胺、联苯类三芳胺、噻吩、并噻吩如二噻吩并噻吩和并噻吩、吡咯、苯胺、咔唑、氮茚并氮芴及它们的衍生物。另外，合适的HIM也包括自组装单体,如含有膦酸和sliane衍生物的化合物；金属络合物和交联化合物等。
电子阻挡层(EBL)用来阻挡来自相邻功能层，特别是发光层的电子。对比一个没有阻挡层的发光器件,EBL的存在通常会导致发光效率的提高。电子阻挡层(EBL)的电子阻挡材料(EBM)需要有比相邻功能层，如发光层更高的LUMO。在一个优先的实施方案中，HBM有比相邻发光层更大的激发态能级,如单重态或三重态,取决于发光体，同时，EBM有空穴传输功能。通常具有高的LUMO能级的HIM/HTM材料可以作为EBM。
可用作HIM，HTM或EBM的环芳香胺衍生化合物的例子包括(但不限于)如下的一般结构：
Figure PCTCN2017112703-appb-000029
每个Ar1到Ar9可独立选自环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、非那烯、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、呋喃、噻吩、苯并呋喃、苯并噻吩、咔唑、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮(杂)萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、二苯并硒吩、苯并硒吩、苯并呋喃吡啶、吲哚咔唑、吡啶吲哚、吡咯二吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起,如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。其中，每个Ar可以进一步被取代，取代基可选为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
在一个方面，Ar1到Ar9可独立选自包含如下组的基团:
Figure PCTCN2017112703-appb-000030
n是1到20的整数；X1到X8是CH或N；Ar1如以上所定义。
环芳香胺衍生化合物的另外的例子可参见US3567450,US4720432,US5061569, US3615404,和US5061569.
可用作HTM或HIM的金属络合物的例子包括(但不限于)如下的一般结构:
Figure PCTCN2017112703-appb-000031
M是一金属,有大于40的原子量；
(Y1-Y2)是一两齿配体,Y1和Y2独立地选自C、N、O、P和S；L是一个辅助配体；m是一整数，其值从1到此金属的最大配位数；m+n是此金属的最大配位数。
在一个实施例中，(Y1-Y2)是2-苯基吡啶衍生物.
在另一个实施例中,(Y1-Y2)是一卡宾配体.
在另一个实施例中,M选于Ir、Pt、Os和Zn.
在另一个方面，金属络合物的HOMO大于-5.5eV(相对于真空能级).
在下面的表中列出合适的可作为HIM/HTM化合物的例子:
Figure PCTCN2017112703-appb-000032
Figure PCTCN2017112703-appb-000033
2.单重态基质材料(Singlet Host)：
单重态主体材料的例子并不受特别的限制，任何有机化合物都可能被用作为主体,只要其单重态能量比发光体,特别是单重态发光体或荧光发光体更高。
作为单重态主体材料使用的有机化合物的例子可选自含有环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起，如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。
在一个实施方案中，单重态主体材料可选于包含至少一个以下基团的化合物：
Figure PCTCN2017112703-appb-000034
其中，R1可相互独立地选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、 杂烷基、芳基和杂芳基；Ar1是芳基或杂芳基，它与上述的HTM中定义的Ar1意义相同；n是一个从0到20的整数；X1-X8选于CH或N；X9和X10选于CR1R2或NR1。
在下面的表中列出一些蒽基单重态主体材料的例子：
Figure PCTCN2017112703-appb-000035
3.单重态发光体(Singlet Emitter)
单重态发光体往往有较长的共轭π电子系统。迄今,已有许多例子，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物，和在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物。
在一个实施方案中,单重态发光体可选自一元苯乙烯胺，二元苯乙烯胺，三元苯乙烯胺，四元苯乙烯胺，苯乙烯膦，苯乙烯醚和芳胺。
一个一元苯乙烯胺是指一化合物,它包含一个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个二元苯乙烯胺是指一化合物,它包含二个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个三元苯乙烯胺是指一化合物,它包含三个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个四元苯乙烯胺是指一化合物,它包含四个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个优选的苯乙烯是二苯乙烯,其可能会进一步被取代。相应的膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指一种化合物，包含三个直接联接氮的无取代或取代的芳香环或杂环系统。这些芳香族或杂环的环系统中至少有一个优先选于稠环系统，并最好有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺。一个芳香蒽胺是指一化合物，其中一个二元芳基胺基团直接联到蒽上,最好是在9的位置上。一个芳香蒽二胺是指一化合物，其中二个二元芳基胺基团直接联到蒽上,最好是在9,10的位置上。芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺的定义类似,其中二元芳基胺基团最好联到芘的1或1,6位置上.
基于乙烯胺及芳胺的单重态发光体的例子,也是优选的例子,可在下述专利文件中找到:WO 2006/000388,WO 2006/058737,WO 2006/000389,WO 2007/065549,WO 2007/115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397A,US 6251531 B1,US 2006/210830 A,EP 1957606 A1和US 2008/0113101 A1特此上述列出的专利文件中的全部内容并入本文作为参考。
基于均二苯乙烯极其衍生物的单重态发光体的例子有US 5121029。
进一步的优选的单重态发光体可选于茚并芴-胺和茚并芴-二胺，如WO 2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO 2008/006449所公开的，二苯并茚并芴-胺和二苯并茚并芴-二胺，如WO2007/140847所公开的。
其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物:蒽如9,10-二(2-萘并蒽)，萘,四苯，氧杂蒽，菲,芘(如2,5,8,11-四-t-丁基苝)，茚并芘，苯撑如(4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)，二茚并芘,十环烯,六苯并苯,芴，螺二芴,芳基芘(如US20060222886)，亚芳香基乙烯(如US5121029，US5130603),环戊二 烯如四苯基环戊二烯,红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM),噻喃,双(吖嗪基)亚胺硼化合物(US 2007/0092753 A1),双(吖嗪基)亚甲基化合物,carbostyryl化合物,噁嗪酮,苯并恶唑,苯并噻唑,苯并咪唑及吡咯并吡咯二酮。一些单重态发光体的材料可在下述专利文件中找到:US 20070252517 A1,US 4769292,US 6020078,US 2007/0252517 A1,US 2007/0252517 A1。特此将上述列出的专利文件中的全部内容并入本文作为参考。
在下面的表中列出一些合适的单重态发光体的例子:
Figure PCTCN2017112703-appb-000036
4.热激发延迟荧光发光材料(TADF材料)
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％)。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穿越，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到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光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(ΔEst)，三线态激子可以通过反系间穿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。器件内量子效率可达到100％。同时材料结构可控，性质稳定，价格便宜无需要贵金属，在OLED领域的应用前景广阔。
TADF材料需要具有较小的单线态-三线态能级差，较好是ΔEst<0.3eV，次好是ΔEst<0.2eV，最好是ΔEst<0.1eV。在一个优先的实施方案中，TADF材料有比较小的ΔEst， 在另一个优先的实施方案中,TADF有较好的荧光量子效率。一些TADF发光的材料可在下述专利文件中找到:CN103483332(A),TW201309696(A),TW201309778(A),TW201343874(A)，TW201350558(A),US20120217869(A1),WO2013133359(A1),WO2013154064(A1),Adachi,et.al.Adv.Mater.,21,2009,4802，Adachi,et.al.Appl.Phys.Lett.,98,2011,083302，Adachi,et.al.Appl.Phys.Lett.,101,2012,093306，Adachi,et.al.Chem.Commun.,48,2012,11392，Adachi,et.al.Nature Photonics,6,2012,253，Adachi,et.al.Nature,492,2012,234，Adachi,et.al.J.Am.Chem.Soc,134,2012,14706，Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311，Adachi,et.al.Chem.Commun.,48,2012,9580，Adachi,et.al.Chem.Commun.,48,2013,10385，Adachi,et.al.Adv.Mater.,25,2013,3319，Adachi,et.al.Adv.Mater.,25,2013,3707，Adachi,et.al.Chem.Mater.,25,2013,3038，Adachi,et.al.Chem.Mater.,25,2013,3766，Adachi,et.al.J.Mater.Chem.C.,1,2013,4599，Adachi,et.al.J.Phys.Chem.A.,117,2013,5607，特此将上述列出的专利或文章文件中的全部内容并入本文作为参考。
在下面的表中列出一些合适的TADF发光材料的例子:
Figure PCTCN2017112703-appb-000037
Figure PCTCN2017112703-appb-000038
Figure PCTCN2017112703-appb-000039
以上出现的有机功能材料出版物为公开的目的以参考方式并入本申请。
一种组合物，包括上述芳香胺衍生物或其高聚物或上述混合物，以及有机溶剂。
在一些实施方案中，所述的氘代芳香胺衍生物作为单重态发光体材料。
在一个实施例中，一种组合物，包含有一种主体材料和上述芳香胺衍生物或其高聚物或上述混合物。
在另一个实施例中，一种组合物，包含有至少两种主体材料和上述芳香胺衍生物或其高聚物或上述混合物。
在另一个实施例中，一种组合物，包含有一种主体材料，一种热激活延迟荧光发光材料和上述芳香胺衍生物或其高聚物或上述混合物。
在另一实施方案中，一种组合物，包含有一种空穴传输材料(HTM)和上述芳香胺衍生物或其高聚物或上述混合物；
在另一实施方案中，一种组合物，包含有一种包含有一可交联基团的空穴传输材料(HTM)和上述芳香胺衍生物或其高聚物或上述混合物。
在一个实施方案中，上述组合物是一溶液。
在另一个实施方案中，上述组合物是一悬浮液。
在一实施例中，组合物中包括0.01wt％～20wt％的上述芳香胺衍生物或其高聚物或上述混合物；
在一实施例中，组合物中包括0.1wt％～15wt％的上述芳香胺衍生物或其高聚物或上述混合物；
在一实施例中，组合物中包括0.2wt％～10wt％的上述芳香胺衍生物或其高聚物或上述混合物；
在一实施例中，组合物中包括0.25wt％～5wt％的上述芳香胺衍生物或其高聚物或上述混合物。
在一实施例中，一种组合物，该组合物中所用的溶剂选自：芳族或杂芳族、酯、芳族酮或芳族醚、脂肪族酮或脂肪族醚、脂环族或烯烃类化合物，或硼酸酯或磷酸酯等无机酯类化合物，或两种及两种以上溶剂的混合物。
在一实施例中，一种组合物，其中包含至少50wt％的芳族或杂芳族溶剂；
在一实施例中，一种组合物，其中包含至少80wt％的芳族或杂芳族溶剂；
在一实施例中，一种组合物，其中包含至少90wt％的的芳族或杂芳族溶剂。
在一实施例中，基于芳族或杂芳族溶剂的例子有，但不限于：1-四氢萘酮、3-苯氧基甲苯、苯乙酮、1-甲氧基萘、对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、二苯醚、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2- 苯基吡啶、3-苯基吡啶、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、N-甲基二苯胺、4-异丙基联苯、-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘、二苄醚等。
在另一些实施例中，适当的和优选的溶剂是脂肪族、脂环族或芳烃族，胺，硫醇，酰胺，腈，酯，醚，聚醚，醇，二醇或多元醇。
在另一些实施例中，醇代表适当类别的溶剂。优选的醇包括烷基环己醇，特别是甲基化的脂肪族醇，萘酚等。
所述的溶剂可以是环烷烃，例如十氢化萘。
所述的溶剂可以是单独使用，也可以是作为两种或多种有机溶剂的混合物使用。
在某些实施例中，上述组合物，包含有一种上述芳香胺衍生物或其高聚物，及至少一种有机溶剂，还可进一步包含另一种有机溶剂，另一种有机溶剂的例子，包括(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚和/或它们的混合物。
在一实施例中，上述组合物中的有机溶剂是汉森(Hansen)溶解度参数在以下范围内的溶剂：
δd(色散力)在17.0～23.2MPa1/2的范围，尤其是在18.5～21.0MPa1/2的范围；
δp(极性力)在0.2～12.5MPa1/2的范围，尤其是在2.0～6.0MPa1/2的范围；
δh(氢键力)在0.9～14.2MPa1/2的范围，尤其是在2.0～6.0MPa1/2的范围。
选取上述组合物中的有机溶剂时需考虑其沸点参数。在一实施例中，所述的有机溶剂的沸点≥1501C；在一实施例中，所述的有机溶剂的沸点≥180℃；在一实施例中，所述的有机溶剂的沸点≥200℃；在一实施例中，所述的有机溶剂的沸点≥250℃；在一实施例中，所述的有机溶剂的沸点≥275℃；在一实施例中，所述的有机溶剂的沸点≥300℃。这些范围内的沸点对防止喷墨印刷头的喷嘴堵塞是有益的。所述的有机溶剂可从溶剂体系中蒸发，以形成包含功能材料薄膜。
在一实施例中，一种组合物，所选用的溶剂的粘度核表面张力如下所述：
1)其粘度@25℃，在1cPs到100cPs范围，和/或
2)其表面张力@25℃，在19dyne/cm到50dyne/cm范围。
在选取上述组合物中有机溶剂时需考虑其表面张力参数。合适的油墨表面张力参数适合于特定的基板和特定的印刷方法。例如对喷墨印刷，在一个实施例中，所述的有机溶剂在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；所述的有机溶剂在25℃下的表面张力约在22dyne/cm到35dyne/cm范围；所述的有机溶剂在25℃下的表面张力约在25dyne/cm到33dyne/cm范围。
在一个实施例中，油墨在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；在一个实施例中，油墨在25℃下的表面张力约在22dyne/cm到35dyne/cm范围；在一个实施例中，油墨在25℃下的表面张力约在25dyne/cm到33dyne/cm范围。
在选取组合物中的有机溶剂时需考虑其油墨的粘度参数。粘度可以通过不同的方法调节，如通过合适的有机溶剂的选取和油墨中功能材料的浓度。在一个实施例中，所述的有机溶剂的粘度低于100cps；在一个实施例中，所述的有机溶剂的粘度低于50cps；在一个实施例中，所述的有机溶剂的粘度为1.5到20cps。这里的粘度是指在印刷时的环境温度下的粘度，一般在15-30℃，较好的是18-28℃，更好是20-25℃，最好是23-25℃。如此配制的组合物将特别适合于喷墨印刷。
在一个实施例中，一种组合物，在25℃下的粘度约在1cps到100cps范围；在一个实施例中，一种组合物，在25℃下的粘度约在1cps到50cps范围；在一个实施例中，一 种组合物，在25℃下的粘度约在1.5cps到20cps范围。
满足上述沸点及表面张力参数及粘度参数的有机溶剂获得的油墨能够形成具有均匀厚度及组成性质的功能材料薄膜。
上述芳香胺衍生物、及其高聚物、组合物在有机电子器件中的应用。
所述有机电子器件可选于有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
一种制备上述电子器件的方法；具体技术方案如下：
将上述上述芳香胺衍生物或其高聚物或混合物以蒸镀的方法于一基板上形成一功能层，或以共蒸镀的方法与至少一种另一有机功能材料一起于一基板上形成一功能层，或将上述的组合物用印刷或涂布的方法涂布于一基板上形成一功能层，其中印刷或涂布的方法可选于(但不限于)喷墨打印，喷印(Nozzle Printing)，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂或移印，狭缝型挤压式涂布等。
上述组合物作为印刷油墨在制备有机电子器件时的用途。在一实施例中，采用打印或涂布的制备方法制备上述有机电子器件。
其中，适合的打印或涂布技术可以为喷墨打印，活版印刷，丝网印刷，浸涂，旋转涂布，刮刀涂布，辊筒印花，扭转辊印刷，平版印刷，柔版印刷，轮转印刷，喷涂，刷涂或移印，狭缝型挤压式涂布等。首选的是凹版印刷，丝网印刷及喷墨印刷。凹版印刷，喷墨印刷将在本发明的实施例中应用。溶液或悬浮液可以另外包括一个或多个组份例如表面活性化合物，润滑剂，润湿剂，分散剂，疏水剂，粘接剂等，用于调节粘度，成膜性能，提高附着性等。有关打印技术，及其对有关溶液的相关要求，如溶剂及浓度，粘度等，的详细信息请参见Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。
在一实施例中，按上所述的制备方法所形成的功能层的厚度在5nm-1000nm。
一种有机电子器件，至少包含一种上述芳香胺衍生物或其高聚物，或至少包含一功能层，该功能层是使用上述组合物制备而成。
在一实施例中，一种有机电子器件包括：阴极、阳极及位于阴极和阳极之间的一个功能层，其中所述的功能层中至少包含一种如上所述的芳香胺衍生物或其高聚物或上述混合物或上述组合物。
在一实施例中，以上所述的有机电子器件是电致发光器件，特别是OLED(如图1所示)，其中包括一基片101，一阳极102，至少一发光层104，一阴极106。
基片101可以是不透明或透明。一个透明的基板可以用来制造一个透明的发光元器件。例如可参见，Bulovic等Nature 1996,380,p29，和Gu等，Appl.Phys.Lett.1996,68,p2606。基片可以是刚性的或弹性的。基片可以是塑料，金属，半导体晶片或玻璃。最好是基片有一个平滑的表面。无表面缺陷的基板是特别理想的选择。在一个优选的实施例中，基片是柔性的，可选于聚合物薄膜或塑料，其玻璃化温度Tg为150℃以上，较好是超过200℃，更好是超过250℃，最好是超过300℃。合适的柔性基板的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。
阳极102可包括一导电金属或金属氧化物，或导电聚合物。阳极可以容易地注入空穴到空穴注入层(HIL)或空穴传输层(HTL)或发光层中。在一个的实施例中，阳极的功函数和发光层中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。阳极材料的例子包括但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。其他合适的阳极材料是已知的，本领域普通技术人员可容易地选择使用。阳极材料可以 使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。在某些实施例中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本发明的器件。
阴极106可包括一导电金属或金属氧化物。阴极可以容易地注入电子到EIL或ETL或直接到发光层中。在一个的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV，较好是小于0.3eV，最好是小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本发明器件的阴极材料。阴极材料的例子包括但不限于：Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包括射频磁控溅射，真空热蒸发，电子束(e-beam)等。
OLED还可以包含其他功能层，如空穴注入层(HIL)或空穴传输层(HTL)103、电子阻挡层(EBL)、电子注入层(EIL)或电子传输层(ETL)105、空穴阻挡层(HBL)。适合用于这些功能层中的材料在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述，特此将此3篇专利文件中的全部内容并入本文作为参考。
在一实施例中，发光器件中的发光层104是通过真空蒸镀，其蒸镀源包含有上述芳香胺衍生物或其高聚物或其组合物或其混合物。
在一实施例中，发光器件中的发光层104是通过打印本发明上述芳香胺衍生物或其高聚物或其组合物或其混合物制备而成。
在一实施例中，电致发光器件的发光波长在300到1000nm之间；在一实施例中，电致发光器件的发光波长在350到900nm之间；在一实施例中，电致发光器件的发光波长在400到800nm之间。
上述有机电子器件在各种电子设备中的应用，包括，但不限于，显示设备，照明设备，光源，传感器等等。
上述有机电子器件的电子设备，包括，但不限于，显示设备，照明设备，光源，传感器等等。
下面将结合具体实施例对本发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
需要说明的是，本发明未注明具体来源的试剂或仪器，为市场购买的常规试剂或仪器。
合成例1：化合物1的合成
Figure PCTCN2017112703-appb-000040
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二溴芘(7.2g,20mmol)、2,7-二甲基-N-苯基萘-1-胺(9.9g,40mmol)、Pd(dba)2(690mg,1.2mmol)、NaOtBu(11.5g,120mmol)、(tBu)3P(730mg,3.6mmol)和无水甲苯200mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(11g,80％)。
合成例2：化合物2的合成
Figure PCTCN2017112703-appb-000041
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二溴芘(6.5g,18mmol)、N-苯基2,7-二苯基萘-1-胺(13.4g,36mmol)、Pd(dba)2(620mg,1.08mmol)、NaOtBu(10.4g,108mmol)、(tBu)3P(650mg,3.24mmol)和无水甲苯200mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(12.7g,75％)。
合成例3：化合物3的合成
Figure PCTCN2017112703-appb-000042
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二异丙基-3,8二溴芘(6.7g,15mmol)、N-(4-异丙基苯基)-2,7-二甲基萘-1-胺(8.7g,30mmol)、Pd(dba)2(520mg,0.9mmol)、NaOtBu(8.6g,90mmol)、(tBu)3P(550mg,2.7mmol)和无水甲苯150mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(10.7g,83％)。合成例4：化合物4的合成
Figure PCTCN2017112703-appb-000043
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二异丙基-3,8二溴芘(8.0g,18mmol)、N-([1,1'-联苯]-2-基)-2,7-二甲基萘-1-胺(11.6g,36mmol)、Pd(dba)2(620mg,1.08mmol)、NaOtBu(10.4g,108mmol)、(tBu)3P(650mg,3.24mmol)和无水甲苯200mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(12.7g,77％)。
合成例5：化合物5的合成
Figure PCTCN2017112703-appb-000044
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二异丙基-3,8二溴芘(4.5g,10mmol)、N-(2,7-二甲基萘-1-基)-二苯并呋喃-4-胺(6.7g,20mmol)、Pd(dba)2(345mg,0.6mmol)、NaOtBu(5.76g,60mmol)、(tBu)3P(360mg,1.8mmol)和无水甲苯100mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(8.3g,87％)。
合成例6：化合物6的合成
Figure PCTCN2017112703-appb-000045
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二溴芘(3.6g,10mmol)、N-(2,7-二苯基萘-1-基)-二苯并呋喃-4-胺(9.2g,20mmol)、Pd(dba)2(345mg,0.6mmol)、NaOtBu(5.76g,60mmol)、(tBu)3P(360mg,1.8mmol)和无水甲苯100mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(8.2g,73％)。
合成例7：化合物7的合成
Figure PCTCN2017112703-appb-000046
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1，6-二异丙基-3，8二溴芘(7.5g，17mmol)、N-(2，7-二甲基萘-1-基)-二苯并呋喃-6-氘-4-胺(11.5g，34mmol)、Pd(dba)2(590mg,1.02mmol)、NaOtBu(9.9g,102mmol)、(tBu)3P(620mg,3.06mmol)和无水甲苯200mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(9.6g,59％)。
合成例8：化合物8的合成
Figure PCTCN2017112703-appb-000047
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二溴芘(5.7g,16mmol)、N-(2,7-二异丙基萘-1-基)-二苯并呋喃-4-胺(12.6g,32mmol)、Pd(dba)2(550mg,0.96mmol)、NaOtBu(5.76g,96mmol)、(tBu)3P(580mg,2.9mmol)和无水甲苯200mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(11.7g,74％)。
合成例9：化合物9的合成
Figure PCTCN2017112703-appb-000048
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二溴芘(5.4g,15mmol)、N-(2,7-二甲基萘-1-基)-9,9-二甲基-芴-2-胺(11g,30mmol)、Pd(dba)2(520mg,0.9mmol)、NaOtBu(8.6g,90mmol)、(tBu)3P(540mg,2.7mmol)和无水甲苯150mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(8.9g,64％)。
合成例10：化合物10的合成
Figure PCTCN2017112703-appb-000049
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二溴芘(5.04g,14mmol)、N-(2,7-二甲基萘-1-基)-4a,9a-二甲基-9-苯基-1,2,3,4,4a,9a-六氢-咔唑-6-胺(12.5g,28mmol)、Pd(dba)2(480mg,0.84mmol)、NaOtBu(8.06g,84mmol)、(tBu)3P(505mg,2.5mmol)和无水甲苯150mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(10.1g,66％)。
对比合成例1：对比化合物1的合成
Figure PCTCN2017112703-appb-000050
在氮气流下带有冷凝管的500mL三口烧瓶中，加入1,6-二溴芘(7.2g,20mmol)、二邻甲苯基胺(7.9g,40mmol)、Pd(dba)2(690mg,1.2mmol)、NaOtBu(11.5g,120mmol)、(tBu)3P(730mg,3.6mmol)和无水甲苯150mL，100℃搅拌过夜。反应结束后，滤出析出的固体，用甲苯和甲醇洗涤得淡黄色固体粉末(10.7g,90％)。
实施例11：OLED器件的制备与表征：
OLED器件各层所使用材料：
HIL：一种三芳胺衍生物；
HTL：一种三芳胺衍生物；
Host:蒽衍生物；
Dopant：化合物1-化合物10、对比化合物1。
具有ITO/HIL(50nm)/HTL(35nm)/Host：5％Dopant(25nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极的OLED器件的制备步骤如下:
a、导电玻璃基片的清洗:首次使用时，可用多种溶剂进行清洗，例如氯仿、酮、异丙醇进行清洗，然后进行紫外臭氧等离子处理；
b、HIL(50nm)，HTL(35nm)，EML(25nm)、ETL(28nm)：在高真空(1×10-6毫巴，mbar)中热蒸镀而成。
c、阴极:LiQ/Al(1nm/150nm)在高真空(1×10-6毫巴)中热蒸镀而成；
d、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
Figure PCTCN2017112703-appb-000051
各OLED器件的电流电压(J-V)特性通过表征设备来表征，同时记录重要的参数如效率，寿命及外部量子效率。经检测，采用化合物1-化合物10作为EML层发光体所制备蓝光器件的色坐标更优于对比化合物1，例如化合物5所制备器件的色坐标为(0.149,0.084)；此外，采用化合物1-化合物10作为EML层发光体所制备蓝光器件的发光效率都在6-8cd/A范围，具有更加优异的发光效率；在器件寿命方面，采用化合物1-化合物10作为EML层发光体所制备蓝光器件的寿命更加优于对比化合物1，例如化合物5所制备器件在1000nits下的T95位1530小时。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (18)

  1. 一种如通式(I)所示的芳香胺衍生物：
    Figure PCTCN2017112703-appb-100001
    其中，
    R1、R2、R3、R4、R5、R6、R7或R8彼此相同或不同，所述R1、R2、R3、R4、R5、R6、R7或R8各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    所述R1、R2、R3、R4、R5、R6、R7或R8中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    所述R1、R2、R3、R4、R5、R6、R7或R8中的一个或多个氢原子可以进一步任选被氘原子取代；
    Ar1、Ar2、Ar3或Ar4彼此相同或不同；所述Ar1、Ar2、Ar3或Ar4中至少有一个是通式(II)所示的基团，其他各自独立地选自：具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    其中Ar1、Ar2、Ar3或Ar4中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系；
    所述Ar1、Ar2、Ar3或Ar4中的一个或多个氢原子可以进一步任选被氘原子取代；
    通式(II)的结构为：
    Figure PCTCN2017112703-appb-100002
    其中，
    R9、R10、R11、R12或R13彼此相同或不同，所述R9、R10、R11、R12、R13各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至 20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤代甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    所述R9、R10、R11、R12或R13中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    Ar5、Ar6相同或不同，所述Ar5或Ar6各自独立地选自：H、或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    Ar5、Ar6中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系；
    所述R9、R10、R11、R12、R13、Ar5、或Ar6中的一个或多个氢原子可以进一步任选被氘原子取代；
    虚线表示与通式(I)相连接的单键。
  2. 根据权利要求1所述的芳香胺衍生物，其特征在于，所述Ar1、Ar2、Ar3或Ar4各自独立地进一步任选如下结构式：
    Figure PCTCN2017112703-appb-100003
    X1是CR7或N；
    Y选自CR8R9，SiR10R11，NR12或，C(＝O)，S，或O；
    R7，R8，R9，R10，R11，R12各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团，氨基甲酰基基团，卤代甲酰基基团,甲酰基基团，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    所述R7，R8，R9，R10，R11或R12中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    所述R7，R8，R9，R10，R11或R12中一个或多个氢原子可以任选进一步被氘原子取代。
  3. 根据权利要求2所述的芳香胺衍生物，其特征在于，所述芳香胺衍生物具有通式(III)所示的结构：
    Figure PCTCN2017112703-appb-100004
    Ar7、Ar8、Ar9、或Ar10彼此相同或不同，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自：H、或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    所述Ar7、Ar8、Ar9、或Ar10可以彼此和/或与所述Ar7、Ar8、Ar9、或Ar10连接的环形成单环或多环的脂族或芳族环系；
    Ar11、Ar12可以相同或不同，所述Ar11、Ar12各自独立地选自：H，具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    所述Ar11、Ar12中一个或多个基团可以彼此和/或与所述基团键合的环形成多环的脂族或芳族环系；
    R14、R15相同或不同，R14或R15各自独立地选自H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤代甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    R14、R15中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    所述R14、R15、Ar7、Ar8、Ar9、Ar10、Ar11或Ar12中的一个或多个H可以任选进一步被D所取代。
  4. 根据权利要求3所述的芳香胺衍生物，其特征在于，所述Ar7、Ar8、Ar9、或Ar10彼此相同或不同，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自：H、D、甲基，乙基，正丙基，异丙基，环丙基，正丁基，异丁基，仲丁基，叔丁基，环丁基，甲基丁基，正戊基，仲戊基，环戊基，正己基，环己基，正庚基，环庚基，正辛基，环辛基，乙基己基，三氟甲基，五氟乙基，三氟乙基，乙烯基，丙烯基，丁烯基，戊烯基，环戊烯基，己烯基，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、辛炔基、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，叔丁氧基或甲基丁氧基、三甲基硅烷，或具有以下结构的取代或未取代芳基或杂芳基：
    Figure PCTCN2017112703-appb-100005
    Y是CR31或N，但没有两个相邻的Y同时为N；
    R31是H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤代甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    R31中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    R31中的一个或多个H可以任选进一步被D所取代；
    虚线表示所述基团与芳香胺的N原子连接的单键。
  5. 根据权利要求4所述的芳香胺衍生物，其特征在于，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自以下所示的结构：
    Figure PCTCN2017112703-appb-100006
    Figure PCTCN2017112703-appb-100007
  6. 根据权利要求4所述的芳香胺衍生物，其特征在于，所述Ar7、Ar8、Ar9、或Ar10各自独立地选自：H、D、甲基、异丙基、异丁基、仲丁基、叔丁基、三甲基硅烷、环戊基、环己基、苯基或5个氢原子被氘原子取代的苯基。
  7. 根据权利要求3所述的芳香胺衍生物，其特征在于，所述Ar11或Ar12各自独立地选自以下所示的结构：
    Figure PCTCN2017112703-appb-100008
    Figure PCTCN2017112703-appb-100009
    Z是CR34或N，但没有两个相邻的Z同时为N；
    R32、R33或R34各自独立地选自：H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    所述R32、R33或R34中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    所述R32、R33或R34中的一个或多个H可以任选进一步被D所取代；
    P是具有3到10个环原子的饱和环烷烃或杂环烷烃；
    虚线表示所述基团与芳香胺的N原子连接的单键。
  8. 根据权利要求7所述的芳香胺衍生物，其特征在于，所述Ar11或Ar12各自独立地选自以下所示的结构：
    Figure PCTCN2017112703-appb-100010
    Figure PCTCN2017112703-appb-100011
  9. 根据权利要求3所述的芳香胺衍生物，其特征在于，R14、R15相同或不同，所述R14、R15各自独立地选自：H、D、甲基，乙基，正丙基，异丙基，环丙基，正丁基，异丁基，仲丁 基，叔丁基，环丁基，甲基丁基，正戊基，仲戊基，环戊基，正己基，环己基，正庚基，环庚基，正辛基，环辛基，乙基己基，三氟甲基，五氟乙基，三氟乙基，乙烯基，丙烯基，丁烯基，戊烯基，环戊烯基，己烯基，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、辛炔基、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，叔丁氧基或甲基丁氧基、三甲基硅烷，或具有以下结构的取代或未取代芳基或杂芳基：
    Figure PCTCN2017112703-appb-100012
    W是CR35或N，但没有两个相邻的W同时为N；
    R35可以是H，或者具有1至20个C原子的直链烷基、或者具有1至20个C原子的烷氧基、或者具有1至20个C原子的硫代烷氧基，或者具有3至20个C原子的支链或环状的烷基、或者具有3至20个C原子的烷氧基、或者具有3至20个C原子的硫代烷氧基，，或者是取代或无取代的甲硅烷基，或具有1至20个C原子的取代的酮基，或具有2至20个C原子的烷氧基羰基，或具有7至20个C原子的芳氧基羰基，氰基，氨基甲酰基，卤甲酰基,甲酰基，异氰基，异氰酸酯，硫氰酸酯或异硫氰酸酯，羟基，硝基，CF3，Cl，Br，F，可交联的基团，或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团；
    R35中一个或多个基团可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环系；
    所述R35中的一个或多个H可以任选进一步被D所取代；
    虚线表示所述基团与其它基团连接的单键。
  10. 根据权利要求9所述的芳香胺衍生物，其特征在于，所述R14、R15各自独立地选自：H、D、异丙基、异丁基、叔丁基、四甲基硅烷或具有以下结构的取代或未取代芳基或杂芳基：
    Figure PCTCN2017112703-appb-100013
    Figure PCTCN2017112703-appb-100014
  11. 根据权利要求10所述的芳香胺衍生物，其特征在于，所述R14和R15相同或不同，所述R14、R15各自独立地选自：H、D、异丙基、异丁基、叔丁基、四甲基硅烷、苯、二联苯、至少含有一个D原子的苯或至少含有一个D原子的二联苯。
  12. 根据权利要求4-11所述的芳香胺衍生物，其特征在于，所述Ar7、Ar8、Ar9、或Ar10彼此相同，所述Ar7、Ar8、Ar9、和Ar10选自：甲基、苯基或异丙基；
    所述Ar11和Ar12彼此相同，所述Ar11和Ar12选自以下所示的取代基：
    Figure PCTCN2017112703-appb-100015
    所述R14、R15彼此相同，所述R14和R15为氢原子或异丙基或异丁基或叔丁基。
  13. 一种高聚物，其特征在于，包含至少一个重复单元，所述重复单元选自权利要求1-12任一项所述的芳香胺衍生物。
  14. 一种混合物，其特征在于，包括权利要求1-12任一项所述的芳香胺衍生物或权利要求13所述的高聚物、以及至少一种有机功能材料，所述有机功能材料选自：空穴注入或传输材料，空穴阻挡材料，电子注入或传输材料，电子阻挡材料，有机基质材料，单重态发光体，三重态发光体、热激发延迟荧光材料及有机染料。
  15. 一种组合物，其特征在于，包括上述权利要求1-12任一项所述的芳香胺衍生物或权利要求13所述的高聚物或权利要求14所述的混合物，以及有机溶剂。
  16. 根据权利要求15所述的组合物，其特征在于，权利要求1-12任一项所述的芳香胺衍生物或权利要求13所述的高聚物或权利要求14所述的混合物所占的重量百分比为0.01wt％～20wt％。
  17. 权利要求1-12任一项所述的芳香胺衍生物或权利要求13所述的高聚物或权利要求14所述的混合物或权利要求15或16所述的组合物在有机电子器件中的应用。
  18. 一种有机电致发光器件，其特征在于，包括：阴极、阳极以及有机层，所述有机层由权利要求1-12任一项所述的芳香胺衍生物或权利要求13所述的高聚物或权利要求14所述的混合物或权利要求15或16所述的组合物所形成。
PCT/CN2017/112703 2016-11-23 2017-11-23 芳香胺衍生物及其制备方法和用途 WO2018095382A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780059206.3A CN109790457B (zh) 2016-11-23 2017-11-23 芳香胺衍生物及其制备方法和用途
US16/463,653 US11512039B2 (en) 2016-11-23 2017-11-23 Aromatic amine derivatives, preparation methods therefor, and uses thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201611048273 2016-11-23
CN201611048273.9 2016-11-23

Publications (1)

Publication Number Publication Date
WO2018095382A1 true WO2018095382A1 (zh) 2018-05-31

Family

ID=62194766

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/112703 WO2018095382A1 (zh) 2016-11-23 2017-11-23 芳香胺衍生物及其制备方法和用途

Country Status (3)

Country Link
US (1) US11512039B2 (zh)
CN (1) CN109790457B (zh)
WO (1) WO2018095382A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108558678A (zh) * 2017-12-29 2018-09-21 广州华睿光电材料有限公司 芳香胺衍生物及有机电子器件
CN112430190A (zh) * 2019-08-26 2021-03-02 北京夏禾科技有限公司 芳香族胺衍生物及包含其的有机电致发光器件

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200111962A1 (en) * 2018-10-03 2020-04-09 Idemitsu Kosan Co., Ltd. Organic electroluminescence device and electronic apparatus provided with the same
CN112430191A (zh) * 2019-08-26 2021-03-02 北京夏禾科技有限公司 包含芳香族胺取代的芘化合物
CN112430189B (zh) * 2019-08-26 2024-03-29 北京夏禾科技有限公司 包含芳香族胺取代的芘类有机电致发光材料
KR20210128268A (ko) * 2020-04-16 2021-10-26 삼성전자주식회사 유기 발광 소자
CN114436862B (zh) * 2020-11-06 2024-02-06 广州华睿光电材料有限公司 芳胺类有机化合物、混合物、组合物及有机电子器件

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008136522A1 (ja) * 2007-05-08 2008-11-13 Idemitsu Kosan Co., Ltd. ジアミノピレン誘導体、および、これを用いた有機ｅｌ素子
WO2009102054A1 (ja) * 2008-02-15 2009-08-20 Idemitsu Kosan Co., Ltd. 有機発光媒体および有機ｅｌ素子
WO2009102026A1 (ja) * 2008-02-15 2009-08-20 Idemitsu Kosan Co., Ltd. 有機発光媒体および有機ｅｌ素子
CN101747889A (zh) * 2008-12-05 2010-06-23 乐金显示有限公司 蓝色荧光化合物及使用该蓝色荧光化合物的有机电致发光器件
CN103165818A (zh) * 2011-12-16 2013-06-19 乐金显示有限公司 有机发光器件
CN103304428A (zh) * 2012-03-06 2013-09-18 三星显示有限公司 胺类化合物、包含胺类化合物的有机发光元件以及有机发光装置
US20150034915A1 (en) * 2013-07-30 2015-02-05 Samsung Display Co., Ltd. Organic light-emitting device
CN105359292A (zh) * 2013-07-17 2016-02-24 罗门哈斯电子材料韩国有限公司 掺杂剂化合物和主体化合物的组合及包含所述组合的有机电致发光装置
CN105514288A (zh) * 2014-10-13 2016-04-20 环球展览公司 新颖化合物和在装置中的用途
CN105810837A (zh) * 2015-01-16 2016-07-27 三星显示有限公司 有机发光器件

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567450A (en) 1968-02-20 1971-03-02 Eastman Kodak Co Photoconductive elements containing substituted triarylamine photoconductors
US3615404A (en) 1968-04-25 1971-10-26 Scott Paper Co 1 3-phenylenediamine containing photoconductive materials
US4720432A (en) 1987-02-11 1988-01-19 Eastman Kodak Company Electroluminescent device with organic luminescent medium
US4769292A (en) 1987-03-02 1988-09-06 Eastman Kodak Company Electroluminescent device with modified thin film luminescent zone
US5121029A (en) 1987-12-11 1992-06-09 Idemitsu Kosan Co., Ltd. Electroluminescence device having an organic electroluminescent element
US5130603A (en) 1989-03-20 1992-07-14 Idemitsu Kosan Co., Ltd. Organic electroluminescence device
US5061569A (en) 1990-07-26 1991-10-29 Eastman Kodak Company Electroluminescent device with organic electroluminescent medium
JP2913116B2 (ja) 1990-11-20 1999-06-28 株式会社リコー 電界発光素子
EP1146034A1 (en) 1995-09-25 2001-10-17 Toyo Ink Manufacturing Co., Ltd. Light-emitting material for organic electroluminescence device, and organic electroluminescence device for which the light-emitting material is adapted
US6020078A (en) 1998-12-18 2000-02-01 Eastman Kodak Company Green organic electroluminescent devices
KR100809132B1 (ko) 1999-09-21 2008-02-29 이데미쓰 고산 가부시키가이샤 유기 전자발광 소자 및 유기 발광 매체
KR20030093240A (ko) 2001-03-16 2003-12-06 이데미쓰 고산 가부시키가이샤 방향족 아미노 화합물의 제조방법
JP4025137B2 (ja) 2002-08-02 2007-12-19 出光興産株式会社 アントラセン誘導体及びそれを利用した有機エレクトロルミネッセンス素子
JP2004075567A (ja) 2002-08-12 2004-03-11 Idemitsu Kosan Co Ltd オリゴアリーレン誘導体及びそれを利用した有機エレクトロルミネッセンス素子
US7839074B2 (en) 2002-08-23 2010-11-23 Idemitsu Kosan Co., Ltd. Organic electroluminescence device and anthracene derivative
US8568902B2 (en) 2003-12-01 2013-10-29 Idemitsu Kosan Co., Ltd. Asymmetric monoanthracene derivative, material for organic electroluminescent device and organic electroluminescent device utilizing the same
EP1696015B1 (en) 2003-12-19 2015-05-13 Idemitsu Kosan Co., Ltd. Light-emitting material for organic electroluminescent device, organic electroluminescent device using same, and material for organic electroluminescent device
US7233019B2 (en) 2004-04-26 2007-06-19 E. I. Du Pont De Nemours And Company Electroluminescent silylated pyrenes, and devices made with such compounds
CN100368363C (zh) 2004-06-04 2008-02-13 友达光电股份有限公司 蒽化合物以及包括此蒽化合物的有机电致发光装置
DE102004031000A1 (de) 2004-06-26 2006-01-12 Covion Organic Semiconductors Gmbh Organische Elektrolumineszenzvorrichtungen
TW200613515A (en) 2004-06-26 2006-05-01 Merck Patent Gmbh Compounds for organic electronic devices
TW200639140A (en) 2004-12-01 2006-11-16 Merck Patent Gmbh Compounds for organic electronic devices
JP4263700B2 (ja) 2005-03-15 2009-05-13 出光興産株式会社 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
US20060222886A1 (en) 2005-04-04 2006-10-05 Raymond Kwong Arylpyrene compounds
KR100701143B1 (ko) 2005-04-04 2007-03-29 후지필름 가부시키가이샤 유기 전계 발광 소자
DE102005023437A1 (de) 2005-05-20 2006-11-30 Merck Patent Gmbh Verbindungen für organische elektronische Vorrichtungen
US20070092753A1 (en) 2005-10-26 2007-04-26 Eastman Kodak Company Organic element for low voltage electroluminescent devices
DE102005058543A1 (de) 2005-12-08 2007-06-14 Merck Patent Gmbh Organische Elektrolumineszenzvorrichtungen
DE102005058557A1 (de) 2005-12-08 2007-06-14 Merck Patent Gmbh Organische Elektrolumineszenzvorrichtung
DE102006015183A1 (de) 2006-04-01 2007-10-04 Merck Patent Gmbh Materialien für organische Elektrolumineszenzvorrichtungen
US20070252517A1 (en) 2006-04-27 2007-11-01 Eastman Kodak Company Electroluminescent device including an anthracene derivative
DE102006025846A1 (de) 2006-06-02 2007-12-06 Merck Patent Gmbh Neue Materialien für organische Elektrolumineszenzvorrichtungen
DE102006031990A1 (de) 2006-07-11 2008-01-17 Merck Patent Gmbh Neue Materialien für organische Elektrolumineszenzvorrichtungen
JP2008053397A (ja) 2006-08-24 2008-03-06 Ricoh Co Ltd 半導体装置及びその製造方法
JP2008124156A (ja) 2006-11-09 2008-05-29 Idemitsu Kosan Co Ltd 有機ｅｌ材料含有溶液、有機ｅｌ材料の薄膜形成方法、有機ｅｌ材料の薄膜、有機ｅｌ素子
US8221905B2 (en) 2007-12-28 2012-07-17 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
US8586203B2 (en) 2009-05-20 2013-11-19 Universal Display Corporation Metal complexes with boron-nitrogen heterocycle containing ligands
KR101368164B1 (ko) 2009-05-29 2014-02-27 이데미쓰 고산 가부시키가이샤 안트라센 유도체 및 그것을 이용한 유기 전계 발광 소자
JP6246468B2 (ja) 2010-03-11 2017-12-13 メルク パテント ゲーエムベーハー 治療および化粧品におけるファイバー
US9783734B2 (en) 2011-02-28 2017-10-10 Kyulux, Inc. Delayed fluorescence material and organic electroluminescence device
WO2013011955A1 (ja) 2011-07-15 2013-01-24 国立大学法人九州大学 遅延蛍光材料およびそれを用いた有機エレクトロルミネッセンス素子
US9660198B2 (en) 2011-07-15 2017-05-23 Kyulux, Inc. Organic electroluminescence element and compound used therein
US9985215B2 (en) 2012-03-09 2018-05-29 Kyulux, Inc. Light-emitting material, and organic light-emitting element
JP2014135466A (ja) 2012-04-09 2014-07-24 Kyushu Univ 有機発光素子ならびにそれに用いる発光材料および化合物
KR20150016242A (ko) 2012-04-25 2015-02-11 고쿠리쓰다이가쿠호진 규슈다이가쿠 발광 재료 및 유기 발광 소자
JP5594750B2 (ja) 2012-05-17 2014-09-24 国立大学法人九州大学 化合物、発光材料および有機発光素子
CN103483332B (zh) 2013-09-11 2016-08-10 中山大学 具有热激活延迟荧光和聚集诱导发光性能的压致发光材料及其合成方法和应用

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008136522A1 (ja) * 2007-05-08 2008-11-13 Idemitsu Kosan Co., Ltd. ジアミノピレン誘導体、および、これを用いた有機ｅｌ素子
WO2009102054A1 (ja) * 2008-02-15 2009-08-20 Idemitsu Kosan Co., Ltd. 有機発光媒体および有機ｅｌ素子
WO2009102026A1 (ja) * 2008-02-15 2009-08-20 Idemitsu Kosan Co., Ltd. 有機発光媒体および有機ｅｌ素子
CN101747889A (zh) * 2008-12-05 2010-06-23 乐金显示有限公司 蓝色荧光化合物及使用该蓝色荧光化合物的有机电致发光器件
CN103165818A (zh) * 2011-12-16 2013-06-19 乐金显示有限公司 有机发光器件
CN103304428A (zh) * 2012-03-06 2013-09-18 三星显示有限公司 胺类化合物、包含胺类化合物的有机发光元件以及有机发光装置
CN105359292A (zh) * 2013-07-17 2016-02-24 罗门哈斯电子材料韩国有限公司 掺杂剂化合物和主体化合物的组合及包含所述组合的有机电致发光装置
US20150034915A1 (en) * 2013-07-30 2015-02-05 Samsung Display Co., Ltd. Organic light-emitting device
CN105514288A (zh) * 2014-10-13 2016-04-20 环球展览公司 新颖化合物和在装置中的用途
CN105810837A (zh) * 2015-01-16 2016-07-27 三星显示有限公司 有机发光器件

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108558678A (zh) * 2017-12-29 2018-09-21 广州华睿光电材料有限公司 芳香胺衍生物及有机电子器件
CN112430190A (zh) * 2019-08-26 2021-03-02 北京夏禾科技有限公司 芳香族胺衍生物及包含其的有机电致发光器件
CN112430190B (zh) * 2019-08-26 2023-04-18 北京夏禾科技有限公司 芳香族胺衍生物及包含其的有机电致发光器件
US11937499B2 (en) 2019-08-26 2024-03-19 Beijing Summer Sprout Technology Co., Ltd. Aromatic amine derivative and organic electroluminescent devices containing the same

Also Published As

Publication number Publication date
CN109790457A (zh) 2019-05-21
US11512039B2 (en) 2022-11-29
US20190315675A1 (en) 2019-10-17
CN109790457B (zh) 2023-06-30

Similar Documents

Publication Publication Date Title
WO2018095382A1 (zh) 芳香胺衍生物及其制备方法和用途
WO2017092508A1 (zh) D-a型化合物及其应用
CN109608342B (zh) 芳香胺衍生物、聚合物、混合物、组合物和有机电子器件
WO2019128633A1 (zh) 含硼杂环化合物、高聚物、混合物、组合物及其用途
WO2019128875A1 (zh) 芳香胺衍生物及有机电子器件
WO2016112762A1 (zh) 化合物、包含其的混合物、组合物和有机电子器件
CN108137604B (zh) 并吡咯衍生物及其在有机电子器件的应用
WO2017118238A1 (zh) 氘代三芳胺衍生物及其在电子器件中的应用
CN109705100B (zh) 含萘咔唑类有机光化合物、混合物、组合物及其用途
US11518723B2 (en) Fused ring compound, high polymer, mixture, composition and organic electronic component
WO2017118137A1 (zh) 咔唑衍生物、高聚物、混合物、组合物、有机电子器件及其应用
WO2018095386A1 (zh) 稠环化合物、高聚物、混合物、组合物以及有机电子器件
US20190006609A1 (en) Organic functional compound for preparing organic electronic device and application thereof
WO2018103744A1 (zh) 混合物、组合物及有机电子器件
CN109790087B (zh) 氘代稠环化合物、高聚物、混合物、组合物以及有机电子器件
WO2018095393A1 (zh) 有机化合物、有机混合物、有机电子器件
WO2017118252A1 (zh) 含砜基稠杂环化合物及其应用
WO2022144018A1 (zh) 有机混合物及其在有机电子器件的应用
WO2022078429A1 (zh) 一种发光器件以及其在显示中的应用
WO2018095383A1 (zh) 氘代芳香胺衍生物及其制备方法和用途
WO2018099432A1 (zh) 稠环化合物及制备方法和应用
WO2018099433A1 (zh) 稠环化合物及其应用、混合物、有机电子器件
CN111279508A (zh) 用于制备有机电子器件的组合物、有机电子器件及应用
WO2018099431A1 (zh) 芘类有机化合物及其制备方法和应用
WO2018108108A1 (zh) 共轭聚合物及其在有机电子器件的应用

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: 17873821

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: 17873821

Country of ref document: EP

Kind code of ref document: A1