WO2023273998A1 - 一种化合物及其应用、一种有机电致发光器件 - Google Patents

一种化合物及其应用、一种有机电致发光器件 Download PDF

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WO2023273998A1
WO2023273998A1 PCT/CN2022/100563 CN2022100563W WO2023273998A1 WO 2023273998 A1 WO2023273998 A1 WO 2023273998A1 CN 2022100563 W CN2022100563 W CN 2022100563W WO 2023273998 A1 WO2023273998 A1 WO 2023273998A1
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substituted
unsubstituted
heteroaryl
aryl
compound
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PCT/CN2022/100563
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French (fr)
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黄金华
黄鑫鑫
方仁杰
董梦青
曾礼昌
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北京鼎材科技有限公司
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Priority to KR1020237045170A priority Critical patent/KR20240026461A/ko
Publication of WO2023273998A1 publication Critical patent/WO2023273998A1/zh

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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • 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
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms
    • 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 application belongs to the technical field of organic electroluminescent materials, and specifically relates to a compound and its application, and an organic electroluminescent device.
  • OLEDs organic light emitting diodes
  • OLED organic field effect transistors
  • organic photovoltaic cells organic sensors, and the like.
  • OLED has developed particularly rapidly and has achieved commercial success in the field of information display.
  • OLED can provide high-saturation red, green, and blue colors, and a full-color display device made of it does not require an additional backlight source, and has the advantages of bright colors, lightness, and softness.
  • the core of an OLED device is a thin film structure containing a variety of organic functional materials.
  • organic functional materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, luminescent host materials and luminescent guest (dye), etc. When electricity is applied, electrons and holes are respectively injected, transported to the light-emitting region, and recombined there, thereby generating excitons and emitting light.
  • Thermally Excited Delayed Fluorescence (TADF) technology promotes the transformation of triplet excitons to singlet excitons, and can still effectively utilize triplet excitons to achieve high luminous efficiency without using metal complexes.
  • Thermally-stimulated sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize light emitters through energy transfer, and can also achieve higher luminous efficiency.
  • the purpose of this application is to provide a compound and its application, an organic electroluminescent device, the compound is applied to an organic electroluminescent device, especially suitable for electron blocking layer materials and/or spacers.
  • the hole transport layer material can improve the luminous efficiency of the device, reduce the driving voltage, and improve the overall performance of the device.
  • X is selected from O, S, CR 1 R 2 , NR 3 or SiR 4 R 5 .
  • Ar 1 and Ar 2 are each independently selected from any one of substituted phenyl, substituted or unsubstituted C9-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; and when Ar 1 contains When , Z 1 is selected from O, S, CR 11 R 12 or NR 13 ; * represents the connecting bond of the group.
  • Ar 3 is selected from any one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , and R 13 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 linear or branched chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 hetero Any one of the aryl groups; R 1 and R 2 , R 4 and R 5 , R 11 and R 12 are each independently unconnected or connected through a chemical bond to form a ring.
  • Rf 1 , R f2 , and R f3 are each independently selected from halogen, cyano, substituted or unsubstituted C1-C20 straight chain or branched chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted Any one of C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.
  • Ar 1 , Ar 2 , Ar 3 , R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 , R f1 , R f2 , and R f3 are each independently is selected from halogen, C1-C10 straight chain or branched chain alkyl, C3-C10 cycloalkyl, C2-C10 heterocycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C30 aryl At least one of amino, C3-C30 heteroarylamino, C6-C30 aryl or C3-C30 heteroaryl.
  • k 1 and k 2 are each independently an integer of 0-3, such as 0, 1, 2 or 3; k 3 is an integer of 0-4, such as 0, 1, 2, 3 or 4.
  • the compound provided by the application has the structure shown in formula I, and the compound has better planarity and aromaticity, is easier to form an amorphous film, reduces the crystallinity of molecules, and makes the spatial structure of the device more compact , so as to reduce the driving voltage and improve the luminous efficiency of the device; at the same time, the N, Ar 1 and Ar 3 of the arylamine structure are respectively connected to the adjacent positions of the benzene ring, making the LUMO energy level of the compound shallower, thereby further blocking excitons Diffusion to the hole layer is more conducive to improving device performance.
  • halogens can all be fluorine, chlorine, bromine or iodine.
  • the following descriptions refer to the same, and all have the same meaning.
  • the "substituted or unsubstituted” group may be substituted with one substituent, or may be substituted with multiple substituents.
  • substituents at least 2
  • they may be the same or different Substituents; when the same expressions are mentioned below, they all have the same meaning, and the selection range of the substituents is as shown above, and will not be repeated one by one.
  • hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H ( tritium, T), etc.
  • carbon (C) includes 12 C, 13 C, etc.
  • heteroatoms of the heteroaryl group are selected from N, O, S, P, B, Si or Se.
  • the expression of the ring structure crossed by "-" indicates that the linking site is at any position on the ring structure that can form a bond.
  • the expression of Ca-Cb means that the number of carbon atoms of the group is a-b, unless otherwise specified, generally speaking, the number of carbon atoms does not include the number of carbon atoms of the substituent.
  • each independently means that when there are plural subjects, they may be the same or different from each other.
  • the C9-C30 aryl group can be C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.
  • the C3-C30 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.
  • the C6-C30 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.
  • the C1-C20 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.
  • the C3-C20 can all be C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 or C19, etc.
  • the C2-C12 can all be C3, C4, C5, C6, C7, C8, C9, C10 or C11, etc.
  • the C1-C10 can all be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.
  • the C3-C10 can all be C3, C4, C5, C6, C7, C8, C9 or C10.
  • the C2-C10 can all be C2, C3, C4, C5, C6, C7, C8, C9 or C10.
  • the C6-C30 aryl group preferably C6-C20 aryl group, includes a single-ring aryl group and a fused-ring aryl group;
  • the single-ring aryl group means that the group contains at least one phenyl group, when containing When there are at least two phenyl groups, the phenyl groups are connected by a single bond, exemplarily including but not limited to: phenyl, biphenyl, terphenyl, etc.
  • the condensed aromatic group means that the group contains at least 2 two aromatic rings, and two adjacent carbon atoms are fused together between the aromatic rings, examples include but not limited to: naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and derivatives thereof (9,9-Dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluoren
  • the C3-C30 heteroaryl includes monocyclic heteroaryl and condensed ring heteroaryl.
  • the monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group.
  • the heteroaryl group and other The groups are connected by a single bond, exemplarily including but not limited to: furyl, thienyl, pyrrolyl, pyridyl and the like.
  • the fused-ring heteroaryl group means a group that contains at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring) in the molecule, and the two share two adjacent atoms that are fused to each other.
  • Exemplary Including but not limited to: benzofuryl, benzothienyl, isobenzofuryl, isobenzothienyl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof (N-phenylcarbazolyl, N-naphthylcarbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl, azacarbazolyl, etc.), acridinyl, Phenothiazinyl, phenoxazinyl, hydrogenated acridinyl, etc.
  • arylene group described below in the present application may include divalent groups obtained by removing one hydrogen atom from the above-mentioned aryl group; specific examples of the heteroarylene group may include the above-mentioned heteroaryl group The divalent group obtained by removing a hydrogen atom in the example.
  • the C1-C20 straight-chain or branched-chain alkyl exemplary includes but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl , isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.
  • the C3-C20 cycloalkyl group exemplarily includes, but is not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and the like.
  • the X is CR 1 R 2 , NR 3 or SiR 4 R 5 , more preferably CR 1 R 2 .
  • the R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from substituted or unsubstituted C1-C6 straight chain or branched chain alkyl, substituted or unsubstituted C6-C18 aryl , any one of substituted or unsubstituted C3-C18 heteroaryl groups; R 1 and R 2 are not connected or are connected to form a ring through a chemical bond, and R 4 and R 5 are not connected or are connected to form a ring through a chemical bond.
  • each of R 1 , R 2 , R 3 , R 4 and R 5 is independently methyl or phenyl.
  • the X is CR 1 R 2 , and the R 1 and R 2 are connected by a chemical bond to form a fluorene ring structure.
  • the Ar is selected from any one of substituted phenyl, substituted or unsubstituted C10-C20 aryl, substituted or unsubstituted C12-C30 heteroaryl; the C12-C30 heteroaryl
  • the heteroatom in is O, S or N.
  • the Ar is selected from any one of the substituted or unsubstituted following groups:
  • * represents the connecting bond of the group
  • R' is selected from halogen, C1-C10 straight chain or branched chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C30 arylamino, C3-C30 heteroaryl Amino, C6-C30 aryl or C3-C30 heteroaryl.
  • Z 1 is selected from O, S, CR 11 R 12 or NR 13 .
  • R 11 , R 12 , and R 13 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 straight chain or branched chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2- Any of C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl.
  • R 11 and R 12 are not connected or connected by a chemical bond to form a ring.
  • n is an integer of 1-5, for example, it can be 1, 2, 3, 4 or 5.
  • the Ar is selected from any one of the substituted or unsubstituted following groups:
  • * represents the connecting bond of the group.
  • the Ar 2 is selected from any one of substituted phenyl, substituted or unsubstituted C10-C20 aryl, substituted or unsubstituted C12-C30 heteroaryl.
  • the Ar is selected from any one of the following substituted or unsubstituted groups :
  • * represents the connecting bond of the group
  • R " is selected from halogen, C1-C10 straight chain or branched chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C30 arylamino, C3-C30 heteroaryl Amino, C6-C30 aryl or C3-C30 heteroaryl;
  • L is selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
  • Z 2 is selected from O, S, CR 21 R 22 , NR 23 or SiR 24 R 25 ;
  • R 21 , R 22 , R 23 , R 24 , and R 25 are each independently selected from hydrogen, substituted or unsubstituted C1-C20 linear or branched chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted Or any of unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;
  • R 21 and R 22 are not connected or are connected to form a ring through a chemical bond, and R 24 and R 25 are not connected or are connected to form a ring through a chemical bond;
  • n is an integer of 1-5, for example, it can be 1, 2, 3, 4 or 5.
  • the L is selected from any one of a single bond, substituted or unsubstituted following groups:
  • * represents the connecting bond of the group.
  • the Ar is selected from any one of the following substituted or unsubstituted groups :
  • L is selected from any of the
  • * represents the linking bond of the group.
  • the Ar 3 is selected from any one of the following substituted or unsubstituted groups:
  • * represents the connecting bond of the group.
  • the R f1 , R f2 , and R f3 are each independently selected from halogen, cyano, substituted or unsubstituted C1-C6 linear or branched chain alkyl, substituted or unsubstituted C3-C6 cycloalkyl , substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C3-C18 heteroaryl.
  • the k 1 , k 2 and k 3 are all 0.
  • substituent groups are each independently selected from halogen, C1-C10 straight chain or branched chain alkyl, C3-C10 cycloalkyl, C2 -C10 heterocycloalkyl, C1-C10 alkoxy, C1-C10 alkylthio, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl or C3-C30 heteroaryl at least one.
  • each of the substituent groups is independently selected from halogen, C1-C10 straight chain or branched chain alkyl, C3-C10 cycloalkyl, C2-C10 heterocycloalkyl, C6-C30 aryl or C3-C30 At least one of heteroaryl.
  • the compound has any one of the following structures shown in P1-P590:
  • the above-mentioned organic compound is selected from the above-mentioned P2, P16, P20, P25, P28, P31, P38, P42, P44, P51, P129, P196, P221, P301, P341, P391, P441, P448 , P461 or P501, when it is applied to an organic electroluminescent device as an electron blocking layer material and/or a hole transporting layer material, it can more effectively improve the luminous efficiency of the device and reduce the driving voltage .
  • the second purpose of the present application is to provide an application of the compound described in the first purpose, which is applied to an organic electroluminescent device.
  • the compounds are used as electron-blocking and/or hole-transporting materials in organic electroluminescent devices.
  • the compounds of the present application can also be applied to lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, sheet type scanners or electronic paper.
  • the third object of the present application is to provide an organic electroluminescence device, which comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode ;
  • the organic layer includes at least one compound as described in one of the purposes.
  • the organic layer includes an electron blocking layer, and the electron blocking layer includes at least one compound according to one of the purposes.
  • the compound provided by the application is applied to an organic electroluminescent device.
  • the driving voltage of the device is significantly reduced, the current efficiency is improved, and the luminescent performance of the organic electroluminescent device is comprehensively improved.
  • the organic layer includes a hole transport layer
  • the hole transport layer includes at least one compound according to one of the purposes.
  • the organic electroluminescent device includes a first electrode and a second electrode, and an organic layer located between the first electrode and the second electrode.
  • the organic layer can be further divided into multiple regions, for example including a hole transport region, a light emitting layer, and an electron transport region.
  • a substrate may be used either below the first electrode or above the second electrode.
  • the substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency.
  • a thin-film transistor (TFT) may be provided on a substrate for a display.
  • the first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate.
  • oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), zinc oxide (ZnO) and any combination thereof can be used.
  • magnesium (Mg) silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In ), magnesium-silver (Mg-Ag) and other metals or alloys and any combination thereof.
  • the organic layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing and other methods.
  • Compounds used as organic layers can be small organic molecules, organic macromolecules or polymers, and combinations thereof.
  • the hole transport region is located between the anode and the light emitting layer.
  • the hole transport region can be a hole transport layer (HTL) with a single-layer structure, including a single-layer hole-transport layer containing only one compound and a single-layer hole-transport layer containing multiple compounds.
  • the hole transport region can also be a multilayer structure comprising at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is positioned between the anode and the HTL, and the EBL It is located between the HTL and the light-emitting layer; the HTL or EBL contains at least one compound with the structure of formula I.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • the material of the hole transport region can also be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene vinylene, polyaniline/dodecylbenzenesulfonic acid ( Pani/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrene sulfonate) (Pani/PSS), aromatic amine derivatives, wherein the aromatic amine derivatives include the following compounds shown in HT-1 to HT-51; or any combination thereof.
  • a hole injection layer is located between the anode and the hole transport layer.
  • the hole injection layer can be a single compound material or a combination of multiple compounds.
  • the hole injection layer can use one or more compounds of the above-mentioned HT-1 to HT-51, or one or more compounds in the following HI-1-HI-3; HT-1 can also be used
  • One or more compounds to HT-51 are doped with one or more compounds in HI-1-HI-3 described below.
  • the luminescent layer includes luminescent dyes (that is, dopant) that can emit different wavelength spectra, and can also include a host material (Host) at the same time.
  • the light-emitting layer may be a monochromatic light-emitting layer that emits a single color such as red, green, or blue.
  • a plurality of monochromatic light-emitting layers of different colors can be arranged planarly according to the pixel pattern, and can also be stacked together to form a colored light-emitting layer. When the light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other.
  • the light-emitting layer can also be a single color light-emitting layer capable of simultaneously emitting different colors such as red, green, and blue.
  • different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and heat-activated delayed fluorescent luminescent materials can be used as materials for the light-emitting layer.
  • a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used.
  • These different luminescent materials classified by technology can emit light of the same color or of different colors.
  • the light-emitting layer adopts fluorescence electroluminescence technology.
  • the fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.
  • the light-emitting layer adopts fluorescence electroluminescence technology.
  • the fluorescent dopant in the light-emitting layer can be selected from, but not limited to, one or more combinations of BFD-1 to BFD-24 listed below.
  • the light-emitting layer adopts phosphorescence electroluminescence technology.
  • the host material of the light-emitting layer is selected from, but not limited to, one or more combinations of PH-1 to PH-85.
  • the light-emitting layer adopts phosphorescence electroluminescence technology.
  • the phosphorescent dopant in the light-emitting layer can be selected from, but not limited to, one or more combinations of GPD-1 to GPD-47 listed below.
  • the light-emitting layer adopts phosphorescence electroluminescence technology.
  • the phosphorescent dopant in the light-emitting layer can be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.
  • the light-emitting layer adopts phosphorescence electroluminescence technology.
  • the phosphorescent dopant in the light-emitting layer can be selected from, but not limited to, one or more combinations of YPD-1 to YPD-11 listed below.
  • the OLED organic layers may also include an electron transport region between the light emitting layer and the cathode.
  • the electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron-transport layer containing only one compound and a single-layer electron-transport layer containing multiple compounds.
  • the electron transport region may also be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the electron transport layer material may be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.
  • a hole blocking layer is located between the electron transport layer and the light emitting layer.
  • Hole blocking layer can adopt, but not limited to, one or more compounds of above-mentioned ET-1 to ET-73, or adopt, but not limited to one or more compounds in PH-1 to PH-46; Mixtures of one or more compounds from ET-1 to ET-73 and one or more compounds from PH-1 to PH-46 are used, but are not limited to.
  • the device may also include an electron injection layer located between the electron transport layer and the cathode, and the materials of the electron injection layer include but are not limited to one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li 2 O, Cs 2 CO 3 , BaO, Na, Li, Ca, Mg or Yb.
  • the thicknesses of the above hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer and electron injection layer are not limited.
  • the thickness of the hole injection layer is preferably 8 to 12 nm
  • the thickness of the hole transport layer is preferably 55 to 65 nm
  • the thickness of the electron blocking layer is preferably 30 to 40 nm.
  • the thickness of the light-emitting layer is 35-45 nm
  • the thickness of the hole blocking layer is preferably 3-8 nm
  • the thickness of the electron transport layer is preferably 20-30 nm
  • the thickness of the electron injection layer is preferably 0.8-1.2 nm.
  • the thickness of the hole injection layer is 10nm
  • the thickness of the hole transport layer is 60nm
  • the thickness of the electron blocking layer is 35nm
  • the thickness of the light-emitting layer is 40nm
  • the thickness of the hole blocking layer is 5nm
  • the thickness of the electron transport layer is When the thickness of the electron injection layer is 25nm and the thickness of the electron injection layer is 1nm, the obtained electroluminescent device has more excellent luminous efficiency and lower driving voltage.
  • the compound provided by this application has the structure shown in formula I, and the compound has better planarity and aromaticity, is easier to form an amorphous film, reduces the crystallinity of molecules, and makes the spatial structure of the device more compact.
  • the N, Ar 1 and Ar 3 of the arylamine structure are respectively connected to the adjacent positions of the benzene ring, so that the LUMO energy level of the compound becomes shallower, thereby further blocking the excitons to the
  • the diffusion of the hole layer is more conducive to improving the performance of the device.
  • the compound is applied to an organic electroluminescence device, especially an electron blocking layer material, which is more conducive to reducing the operating voltage of the device, improving luminous efficiency, and meeting the demand for continuous improvement of the photoelectric performance of the OLED device.
  • Ar 1 , Ar 2 , Ar 3 , X, R f1 , R f2 , R f3 , k 1 , k 2 , and k 3 have the same meanings as in formula I;
  • Pd(PPh 3 ) 4 represents tetrakistriphenyl Palladium phosphine
  • Pd 2 (dba) 3 represents tris(dibenzylacetone) dipalladium (0)
  • Sphos represents 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl
  • IPr.HCl represents 1 , 3-bis(2,6-diisopropylphenyl) imidazolium chloride
  • NaOBu-t represents sodium tert-butoxide
  • (t-Bu) 3 P represents tri-tert-butylphosphine.
  • synthesis examples in this application exemplarily provide specific synthesis methods of the compounds.
  • the solvents and reagents used in the following synthesis examples can be purchased or customized from the chemical product market.
  • those skilled in the art can also synthesize by other known methods.
  • the mass spectrometric characterization data in the following synthesis examples were obtained by testing with a ZAB-HS mass spectrometer manufactured by Micromass, UK.
  • M1-1 m/z theoretical value: 309; m/z measured value: 310.
  • M1-2 m/z theoretical value: 351; m/z measured value: 352.
  • M1-3 m/z theoretical value: 321; m/z measured value: 322.
  • M1-4 m/z theoretical value: 513; m/z measured value: 514.
  • a kind of organic electroluminescence device comprises anode (ITO), hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, electron injection layer and negative electrode (Al ).
  • ITO anode
  • hole injection layer hole transport layer
  • electron blocking layer hole blocking layer
  • light-emitting layer hole blocking layer
  • electron transport layer electron injection layer
  • negative electrode Al
  • the preparation method of the organic electroluminescent device is as follows: the glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, and ultrasonically degreased in a mixed solvent of acetone/ethanol.
  • Example 2 An organic electroluminescent device, the only difference from Example 1 is that the material compound P2 of the electron blocking layer is replaced by the compounds in Table 2.
  • the structure of the electron blocking layer material of Comparative Examples 1-5 is as follows:
  • the source of the above compound CCP-1 can refer to the prior art CN109485577A
  • the source of CCP-2 can refer to the prior art KR1020180104911A
  • the preparation method of CCP-3 is shown in Table 1
  • the source of CCP-4 can refer to the prior art CN107017348A
  • the source of CCP-5 can refer to prior art CN110903276A.
  • the compound provided by the application is used in organic electroluminescent devices, which is more conducive to reducing the turn-on voltage and improving the current efficiency, so that the driving voltage of the device is as low as 3.9-4.3V, and the current efficiency reaches 64.9-69.4 cd/A is a green photoelectron blocking layer material with good performance.
  • the difference between the CCP-1 of Comparative Example 1 and the compound P129 in Example 11 is that the group Ar connected on the N is a phenyl group, which makes the planarity and aromaticity of CCP-1 poor, and affects the crystallinity and The compactness of the spatial structure leads to the high driving voltage and low current efficiency of the device in Comparative Example 1.
  • the difference between the compound CCP-2 of Comparative Example 2 and the compound P51 of Example 10 is that the group Ar1 at the ortho position of the arylamine N on the benzene ring is a phenyl group, which makes the crystallinity of CCP-2 higher and the compactness of the spatial structure poor performance, resulting in poor performance of the device of Comparative Example 2.
  • the application illustrates a compound of the application and its application, and an organic electroluminescent device through the above examples, but the application is not limited to the above examples, that is, it does not mean that the application must rely on the above-mentioned Examples can be implemented.
  • Those skilled in the art should understand that any improvement to the present application, the equivalent replacement of each raw material of the product of the present application, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Abstract

本申请提供一种化合物及其应用、一种有机电致发光器件，所述化合物具有如式I所示结构，具有更好的平面性和芳香性，更易于形成无定形的薄膜，降低分子的结晶性，使器件的空间结构变得更加致密，从而降低驱动电压并提高器件发光效率；同时，芳胺结构的N、Ar 1和Ar 2分别连接于苯环的相邻位置，使所述化合物的LUMO能级变浅，从而进一步阻挡激子向空穴层扩散，使器件性能提高。所述化合物应用于有机电致发光器件，尤其适用于电子阻挡层材料，可以有效降低器件的工作电压，提升发光效率，满足OLED器件的光电性能不断提升的需求。

Description

一种化合物及其应用、一种有机电致发光器件
相关申请的交叉引用
本申请要求在2021年06月28日提交中国专利局、申请号为202110719948.2、申请名称为“一种化合物及其应用、一种有机电致发光器件”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于有机电致发光材料技术领域，具体涉及一种化合物及其应用、一种有机电致发光器件。
背景技术
近年来，基于有机材料的光电子器件已经变得越来越受欢迎。有机材料固有的柔性使其十分适合用于在柔性基板上制造，可根据需求设计、生产出美观而炫酷的光电子产品，获得相对于无机材料无以比拟的优势。此类有机光电子器件的示例包括有机发光二极管(OLED)、有机场效应管、有机光伏电池、有机传感器等。其中，OLED发展尤其迅速，已经在信息显示领域取得商业上的成功。OLED可以提供高饱和度的红、绿、蓝三颜色，用其制成的全色显示装置无需额外的背光源，具有色彩炫丽、轻薄柔软等优点。
OLED器件的核心为含有多种有机功能材料的薄膜结构。常见的有机功能材料有：空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料，电子阻挡材料、发光主体材料和发光客体(染料)等。通电时，电子和空穴被分别注入、传输到发光区域并在此复合，从而产生激子并发光。
目前，人们已经开发出多种有机材料，结合各种新颖的器件结构，可以提升载流子迁移率、调控载流子平衡、突破电致发光效率、延缓器件衰减。出于量子力学的原因，常见的荧光发光体主要利用电子和空穴结合时产生的单线态激子发光，现在仍然广泛地应用于各种OLED产品中。有些金属络合物(例如铱络合物)，可以同时利用三线态激子和单线态激子进行发光，被称为磷光发光体，其能量转换效率可以比传统的荧光发光体提升高达4倍。热激发延迟荧光(TADF)技术通过促进三线态激子朝单线态激子的转变，在不采用金属配合物的情况下，仍然可以有效地利用三线态激子而实现较高的发光效率。热激发敏化荧光(TASF)技术则采用具TADF性质的材料，通过能量转移的方式来敏化发光体，同样可以实现较高的发光效率。
随着OLED产品逐步进入市场，人们对这类产品的性能有越来越高的要求。当前使用的OLED材料和器件结构无法完全解决OLED产品效率、寿命、成本等各方面的问题。
因此，本领域亟待开发一种能够提高器件发光效率、降低驱动电压的有机电致发光材料。
发明内容
针对现有技术的不足，本申请的目的在于提供一种化合物及其应用、一种有机电致发光器件，所述化合物应用于有机电致发光器件，尤其适用于电子阻挡层材料和/或空穴传输层材料，可以提升器件的发光效率，降低驱动电压，改善器件的综合性能。
为达此目的，本申请采用以下技术方案：
本申请的目的之一在于提供一种化合物，所述化合物具有如式I所示结构：
Figure PCTCN2022100563-appb-000001
式I中，X选自O、S、CR 1R 2、NR 3或SiR 4R 5。
式I中，Ar 1、Ar 2各自独立地选自取代的苯基、取代或未取代的C9-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；且当Ar 1包含
Figure PCTCN2022100563-appb-000002
时，Z 1选自O、S、CR 11R 12或NR 13；*代表基团的连接键。
式I中，Ar 3选自取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种。
R 1、R 2、R 3、R 4、R 5、R 11、R 12、R 13各自独立地选自氢、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；R 1和R 2、R 4和R 5、R 11和R 12各自独立地不连接或通过化学键连接成环。
Rf 1、R f2、R f3各自独立地选自卤素、氰基、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种。
Ar 1、Ar 2、Ar 3、R 1、R 2、R 3、R 4、R 5、R 11、R 12、R 13、R f1、R f2、R f3中所述取代的取代基各自独立地选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C2-C10杂环烷基、C1-C10烷氧基、C1-C10烷硫基、C6-C30芳基氨基、C3-C30杂芳基氨基、C6-C30芳基或C3-C30杂芳基中的至少一种。
k 1、k 2各自独立地为0-3的整数，例如可以为0、1、2或3；k 3为0-4的整数，例如可以为0、1、2、3或4。
本申请提供的化合物具有如式I所示结构，所述化合物具有更好的平面性和芳香性，更易于形成无定形的薄膜，降低分子的结晶性，并使器件的空间结构变得更加致密，从而降低驱动电压并提高器件发光效率；同时，芳胺结构的N、Ar 1和Ar 3分别连接于苯环的相邻位置，使所述化合物的LUMO能级变浅，从而进一步阻挡激子向空穴层扩散，更有利于提高器件性能。
需要说明的是，本申请中为了便于说明对各个基团/特征可能的作用分别进行了描述，但这并不表示这些基团/特征是孤立地起作用的。实际上，获得良好性能的原因本质上是整个分子的优化组合，是各个基团之间协同作用的结果，而不是单一基团的效果。
本申请中，所述卤素均可以为氟、氯、溴或碘。下文涉及到相同的描述，均具有相同的含义。
本申请中，所述“取代或未取代”的基团，可以取代有一个取代基，也可以取代有多个取代基，当取代基为多个(至少2个)时，可以为相同或不同的取代基；下文涉及到相同的表达方式时，均具有同样的含义，且取代基的选择范围均如上所示，不再一一赘述。
本申请中，对于化学元素的表述，若无特别说明，则包含化学性质相同的同位素的概念，例如，氢(H)则包括 1H(氕)、 2H(氘，D)、 3H(氚，T)等；碳(C)则包括 12C、 13C等。
本申请中，如无特别说明，杂芳基的杂原子选自N、O、S、P、B、Si或Se。
本申请中，“-”划过的环结构的表达方式，表示连接位点于该环结构上任意能够成键的位置。
在本申请中，Ca-Cb的表达方式代表该基团具有的碳原子数为a-b，除非特殊说明，一般而言该碳原子数不包括取代基的碳原子数。
在本说明书中，“各自独立地”表示其主语具有多个时，彼此之间可以相同也可以不同。
本申请中，所述C9-C30芳基均可以为C9、C10、C12、C14、C16、C18、C20、C22、C24、C26或C28等。
所述C3-C30均可以为C3、C4、C5、C6、C9、C10、C12、C14、C16、C18、C20、C22、C24、C26或C28等。
所述C6-C30均可以为C6、C9、C10、C12、C14、C16、C18、C20、C22、C24、C26或C28等。
所述C1-C20均可以为C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18或C19等。
所述C3-C20均可以为C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18或C19等。
所述C2-C12均可以为C3、C4、C5、C6、C7、C8、C9、C10或C11等。
所述C1-C10均可以为C1、C2、C3、C4、C5、C6、C7、C8、C9或C10。
所述C3-C10均可以为C3、C4、C5、C6、C7、C8、C9或C10。
所述C2-C10均可以为C2、C3、C4、C5、C6、C7、C8、C9或C10。
本申请中，所述C6-C30芳基，优选C6-C20芳基，包括单环芳基和稠环芳基；所述单环芳基意指基团中含有至少1个苯基，当含有至少2个苯基时，苯基之间通过单键相连，示例性地包括但不限于：苯基、联苯基、三联苯基等；所述稠环芳基意指基团中含有至少2个芳环，且芳环之间共用两个相邻的碳原子互相稠合的基团，示例性地包括但不限于：萘基、蒽基、菲基、茚基、芴基及其衍生物(9，9-二甲基芴基、9，9-二乙基芴基、9，9-二丙基芴基、9，9-二丁基芴基、9，9-二戊基芴基、9，9-二己基芴基、9，9-二苯基芴基、9，9-二萘基芴基、螺二芴基、苯并芴基等)、荧蒽基、三亚苯基、芘基、苝基、
Figure PCTCN2022100563-appb-000003
基或并四苯基等。
所述C3-C30杂芳基，包括单环杂芳基和稠环杂芳基。所述单环杂芳基意指分子中含有至少一个杂芳基，当分子中含有一个杂芳基和其他基团(如芳基、杂芳基、烷基等)时，杂芳基和其他基团之间通过单键进行连接，示例性地包括但不限于：呋喃基、噻吩基、吡咯基、吡啶基等。所述稠环杂芳基意指分子中至少含有一个芳杂环和一个芳香性环(芳杂环或芳环)，且二者共用两个相邻的原子互相稠合的基团，示例性地包括但不限于：苯并呋喃基、苯并噻吩基、异苯并呋喃基、异苯并噻吩基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基及其衍生物(N-苯基咔唑基、N-萘基咔唑基、苯并咔唑基、二苯并咔唑基、吲哚并咔唑基、氮杂咔唑基等)、吖啶基、吩噻嗪基、吩恶嗪基、氢化吖啶基等。
本申请下文所述亚芳基的具体例，可以举出上述芳基的例子中去掉一个氢原子而得到的二价基团；所述亚杂芳基的具体例，可以举出上述杂芳基的例子中去掉一个氢原子而得到的二价基团。
所述C1-C20直链或支链烷基，示例性地包括但不限于：甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、正己基、正辛基、正庚基、正壬基、正癸基等。
所述C3-C20环烷基，示例性地包括但不限于：环丙基、环丁基、环戊基、环己基、金刚烷基等。
优选地，所述X为CR 1R 2、NR 3或SiR 4R 5，进一步优选为CR 1R 2。
优选地，所述R 1、R 2、R 3、R 4、R 5各自独立地选自取代或未取代的C1-C6直链或支链烷基、取代或未取代的C6-C18芳基、取代或未取代的C3-C18杂芳基中的任意一种；R 1和R 2不连接或通过化学键连接成环，R 4和R 5不连接或通过化学键连接成环。
优选地，所述R 1、R 2、R 3、R 4、R 5各自独立地为甲基或苯基。
示例性地，所述X为CR 1R 2，所述R 1和R 2通过化学键连接成芴环结构。
优选地，所述Ar 1选自取代的苯基、取代或未取代的C10-C20芳基、取代或未取代的C12-C30杂芳基中的任意一种；所述C12-C30杂芳基中的杂原子为O、S或N。
优选地，所述Ar 1选自取代或未取代的如下基团中的任意一种：
Figure PCTCN2022100563-appb-000004
其中，*代表基团的连接键；
R′选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10烷硫基、C6-C30芳基氨基、C3-C30杂芳基氨基、C6-C30芳基或C3-C30杂芳基。
Z 1选自O、S、CR 11R 12或NR 13。
R 11、R 12、R 13各自独立地选自氢、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种。
R 11和R 12不连接或通过化学键连接成环。
n为1-5的整数，例如可以为1、2、3、4或5。
优选地，所述Ar 1选自取代或未取代的如下基团中的任意一种：
Figure PCTCN2022100563-appb-000005
Figure PCTCN2022100563-appb-000006
其中，*代表基团的连接键。
优选地，所述Ar 2选自取代的苯基、取代或未取代的C10-C20芳基、取代或未取代的C12-C30杂芳基中的任意一种。
优选地，所述Ar 2选自取代或未取代的如下基团中的任意一种：
Figure PCTCN2022100563-appb-000007
其中，*代表基团的连接键；
R″选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10烷硫基、C6-C30芳基氨基、C3-C30杂芳基氨基、C6-C30芳基或C3-C30杂芳基；
L选自单键、取代或未取代的C6-C30亚芳基、取代或未取代的C3-C30亚杂芳基中的任意一种；
Z 2选自O、S、CR 21R 22、NR 23或SiR 24R 25；
R 21、R 22、R 23、R 24、R 25各自独立地选自氢、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；
R 21和R 22不连接或通过化学键连接成环，R 24和R 25不连接或通过化学键连接成环；
m为1-5的整数，例如可以为1、2、3、4或5。
优选地，所述L选自单键、取代或未取代的如下基团中的任意一种：
Figure PCTCN2022100563-appb-000008
其中，*代表基团的连接键。
优选地，所述Ar 2选自取代或未取代的如下基团中的任意一种：
Figure PCTCN2022100563-appb-000009
其中，L选自
Figure PCTCN2022100563-appb-000010
Figure PCTCN2022100563-appb-000011
中的任意一种；
*代表基团的连接键。
优选地，所述Ar 3选自取代或未取代的如下基团中的任意一种：
Figure PCTCN2022100563-appb-000012
Figure PCTCN2022100563-appb-000013
其中，*代表基团的连接键。
优选地，所述R f1、R f2、R f3各自独立地选自卤素、氰基、取代或未取代的C1-C6直链或支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C18芳基、取代或未取代的C3-C18杂芳基中的任意一种。
优选地，所述k 1、k 2、k 3均为0。
本申请前述提及的“取代或未取代”中存在取代基团时，所述取代基团各自独立地选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C2-C10杂环烷基、C1-C10烷氧基、C1-C10烷硫基、C6-C30芳基氨基、C3-C30杂芳基氨基、C6-C30芳基或C3-C30杂芳基中的至少一种。
优选地，所述取代基团各自独立地选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C2-C10杂环烷基、C6-C30芳基或C3-C30杂芳基中的至少一种。
优选地，所述化合物具有如下P1-P590所示的结构中的任意一种：
Figure PCTCN2022100563-appb-000014
Figure PCTCN2022100563-appb-000015
Figure PCTCN2022100563-appb-000016
Figure PCTCN2022100563-appb-000017
Figure PCTCN2022100563-appb-000018
Figure PCTCN2022100563-appb-000019
Figure PCTCN2022100563-appb-000020
Figure PCTCN2022100563-appb-000021
Figure PCTCN2022100563-appb-000022
Figure PCTCN2022100563-appb-000023
Figure PCTCN2022100563-appb-000024
Figure PCTCN2022100563-appb-000025
Figure PCTCN2022100563-appb-000026
Figure PCTCN2022100563-appb-000027
Figure PCTCN2022100563-appb-000028
Figure PCTCN2022100563-appb-000029
Figure PCTCN2022100563-appb-000030
Figure PCTCN2022100563-appb-000031
Figure PCTCN2022100563-appb-000032
Figure PCTCN2022100563-appb-000033
Figure PCTCN2022100563-appb-000034
Figure PCTCN2022100563-appb-000035
Figure PCTCN2022100563-appb-000036
Figure PCTCN2022100563-appb-000037
Figure PCTCN2022100563-appb-000038
Figure PCTCN2022100563-appb-000039
Figure PCTCN2022100563-appb-000040
Figure PCTCN2022100563-appb-000041
Figure PCTCN2022100563-appb-000042
Figure PCTCN2022100563-appb-000043
Figure PCTCN2022100563-appb-000044
Figure PCTCN2022100563-appb-000045
Figure PCTCN2022100563-appb-000046
Figure PCTCN2022100563-appb-000047
Figure PCTCN2022100563-appb-000048
Figure PCTCN2022100563-appb-000049
Figure PCTCN2022100563-appb-000050
Figure PCTCN2022100563-appb-000051
Figure PCTCN2022100563-appb-000052
在本申请的一些实施例中，上述有机化合物选自上述P2、P16、P20、P25、P28、P31、P38、P42、P44、P51、P129、P196、P221、P301、P341、P391、P441、P448、P461或P501中的任意一种或多种的混合物时，其应用于有机电致发光器件作为电子阻挡层材料和/或空穴传输层材料，能够更有效提升器件的发光效率和降低驱动电压。
本申请的目的之二在于提供一种如目的之一所述的化合物的应用，所述化合物应用于有机电致发光器件。
优选地，所述化合物在有机电致发光器件中作为电子阻挡材料和/或空穴传输材料。
除了有机电致发光器件，本申请的化合物还可以应用于照明元件、有机薄膜晶体管、有机场效应晶体管、有机薄膜太阳能电池、信息标签、电子人工皮肤片材、片材型扫描器或电子纸。
本申请的目的之三在于提供一种有机电致发光器件，所述有机电致发光器件包括第一电极、第二电极以及设置于所述第一电极与第二电极之间的至少一个有机层；所述有机层中包括至少一种如目的之一所述的化合物。
优选地，所述有机层包括电子阻挡层，所述电子阻挡层中包括至少一种如目的之一所述的化合物。
本申请提供的化合物应用于有机电致发光器件，其作为电子阻挡层材料时，使器件的驱动电压显著降低，电流效率提高，全面提高了有机电致发光器件的发光性能。
优选地，所述有机层包括空穴传输层，所述空穴传输层中包括至少一种如目的之一所述的化合物。
在一个具体技术方案中，所述有机电致发光器件(OLED)包括第一电极和第二电极，以及位于第一电极和第二电极之间的有机层。所述有机层又可以分为多个区域，例如包括空穴传输区、发光层、电子传输区。
在具体实施方式中，在第一电极下方或者第二电极上方可以使用基板。基板均为具有机械强度、热稳定性、防水性、透明度优异的玻璃或聚合物材料。此外，作为显示器用的基板上也可以带有薄膜晶体管(TFT)。
第一电极可以通过在基板上溅射或者沉积用作第一电极的材料的方式来形成。当第一 电极作为阳极时，可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO 2)、氧化锌(ZnO)等氧化物透明导电材料和它们的任意组合。第一电极作为阴极时，可以采用镁(Mg)、银(Ag)、铝(Al)、铝-锂(Al-Li)、钙(Ca)、镱(Yb)、镁-铟(Mg-In)、镁-银(Mg-Ag)等金属或合金以及它们之间的任意组合。
有机层可以通过真空热蒸镀、旋转涂敷、打印等方法形成于电极之上。用作有机层的化合物可以为有机小分子、有机大分子或聚合物，以及它们的组合。
空穴传输区位于阳极和发光层之间。空穴传输区可以为单层结构的空穴传输层(HTL)，包括只含有一种化合物的单层空穴传输层和含有多种化合物的单层空穴传输层。空穴传输区也可以为包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)中的至少一层的多层结构；其中HIL位于阳极和HTL之间，EBL位于HTL与发光层之间；HTL或EBL中含有至少一种具有式I结构的化合物。
空穴传输区的材料还可以选自、但不限于酞菁衍生物如CuPc、导电聚合物或含导电掺杂剂的聚合物如聚苯撑乙烯、聚苯胺/十二烷基苯磺酸(Pani/DBSA)、聚(3，4-乙撑二氧噻吩)/聚(4-苯乙烯磺酸盐)(PEDOT/PSS)、聚苯胺/樟脑磺酸(Pani/CSA)、聚苯胺/聚(4-苯乙烯磺酸盐)(Pani/PSS)、芳香胺衍生物，其中芳香胺衍生物包括如下HT-1至HT-51所示的化合物；或者其任意组合。
Figure PCTCN2022100563-appb-000053
Figure PCTCN2022100563-appb-000054
Figure PCTCN2022100563-appb-000055
空穴注入层位于阳极和空穴传输层之间。空穴注入层可以是单一化合物材料，也可以 是多种化合物的组合。例如，空穴注入层可以采用上述HT-1至HT-51的一种或多种化合物，或者采用下述HI-1-HI-3中的一种或多种化合物；也可以采用HT-1至HT-51的一种或多种化合物掺杂下述HI-1-HI-3中的一种或多种化合物。
Figure PCTCN2022100563-appb-000056
发光层包括可以发射不同波长光谱的发光染料(即掺杂剂，dopant)，还可以同时包括主体材料(Host)。发光层可以是发射红、绿、蓝等单一颜色的单色发光层。多种不同颜色的单色发光层可以按照像素图形进行平面排列，也可以堆叠在一起而形成彩色发光层。当不同颜色的发光层堆叠在一起时，它们可以彼此隔开，也可以彼此相连。发光层也可以是能同时发射红、绿、蓝等不同颜色的单一彩色发光层。
根据不同的技术，发光层材料可以采用荧光电致发光材料、磷光电致发光材料、热活化延迟荧光发光材料等不同的材料。在一个OLED器件中，可以采用单一的发光技术，也可以采用多种不同的发光技术的组合。这些按技术分类的不同发光材料可以发射同种颜色的光，也可以发射不同种颜色的光。
在本申请的一方面，发光层采用荧光电致发光的技术。其发光层荧光主体材料可以选自、但不限于以下所列举的BFH-1至BFH-17的一种或多种的组合。
Figure PCTCN2022100563-appb-000057
在本申请的一方面，发光层采用荧光电致发光的技术。其发光层荧光掺杂剂可以选自、但不限于以下所列举的BFD-1至BFD-24的一种或多种的组合。
Figure PCTCN2022100563-appb-000058
Figure PCTCN2022100563-appb-000059
在本申请的一方面，发光层采用磷光电致发光的技术。其发光层主体材料选自、但不限于PH-1至PH-85中的一种或多种的组合。
Figure PCTCN2022100563-appb-000060
Figure PCTCN2022100563-appb-000061
Figure PCTCN2022100563-appb-000062
Figure PCTCN2022100563-appb-000063
在本申请的一方面，发光层采用磷光电致发光的技术。其发光层磷光掺杂剂可以选自、但不限于以下所列举的GPD-1至GPD-47的一种或多种的组合。
Figure PCTCN2022100563-appb-000064
Figure PCTCN2022100563-appb-000065
在本申请的一方面，发光层采用磷光电致发光的技术。其发光层磷光掺杂剂可以选自、但不限于以下所列举的RPD-1至RPD-28的一种或多种的组合。
Figure PCTCN2022100563-appb-000066
Figure PCTCN2022100563-appb-000067
在本申请的一方面，发光层采用磷光电致发光的技术。其发光层磷光掺杂剂可以选自、但不限于以下所列举的YPD-1至YPD-11的一种或多种的组合。
Figure PCTCN2022100563-appb-000068
OLED有机层还可以包括发光层与阴极之间的电子传输区。电子传输区可以为单层结构的电子传输层(ETL)，包括只含有一种化合物的单层电子传输层和含有多种化合物的单层电子传输层。电子传输区也可以为包括电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL) 中的至少一层的多层结构。
本申请的一方面，电子传输层材料可以选自、但不限于以下所列举的ET-1至ET-73的一种或多种的组合。
Figure PCTCN2022100563-appb-000069
Figure PCTCN2022100563-appb-000070
Figure PCTCN2022100563-appb-000071
Figure PCTCN2022100563-appb-000072
本申请的一方面，空穴阻挡层(HBL)位于电子传输层与发光层之间。空穴阻挡层可以采用、但不限于上述ET-1至ET-73的一种或多种化合物，或者采用、但不限于PH-1至PH-46中的一种或多种化合物；也可以采用、但不限于ET-1至ET-73的一种或多种化合物与PH-1至PH-46中的一种或多种化合物之混合物。
器件中还可以包括位于电子传输层与阴极之间的电子注入层，电子注入层材料包括但不限于以下列举的一种或多种的组合：LiQ、LiF、NaCl、CsF、Li 2O、Cs 2CO 3、BaO、Na、Li、Ca、Mg或Yb。
上述空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层以及电子注入层的厚度均不作限制。为了进一步提高发光器件的发光效率以及进一步降低驱动电压，优选空穴注入层的厚度为8～12nm，优选空穴传输层的厚度为55～65nm，优选电子阻挡层的厚度为30～40nm，优选发光层的厚度为35～45nm，优选空穴阻挡层的厚度为3～8nm，优选电子传输层的厚度为20～30nm，优选电子注入层的厚度为0.8～1.2nm。尤其是当空穴注入层的厚度为10nm，空穴传输层的厚度为60nm，电子阻挡层的厚度为35nm，发光层的厚度为40nm，空穴阻挡层的厚度为5nm，电子传输层的厚度为25nm，电子注入层的厚度为1nm时，得到的电致发光器件具有更为优异的发光效率和更低的驱动电压。
相对于现有技术，本申请具有以下有益效果：
本申请提供的化合物具有如式I所示结构，所述化合物具有更好的平面性和芳香性，更易于形成无定形的薄膜，降低分子的结晶性，使器件的空间结构变得更加致密，从而降低驱动电压并提高器件发光效率；同时，芳胺结构的N、Ar 1和Ar 3分别连接于苯环的相邻位置，使所述化合物的LUMO能级变浅，从而进一步阻挡激子向空穴层扩散，更有利于提高器件性能。所述化合物应用于有机电致发光器件，尤其适用于电子阻挡层材料，更有利于降低器件的工作电压，提升发光效率，满足OLED器件的光电性能不断提升的需求。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
本申请中，具有式I所示结构的化合物的代表合成路径如下所示：
Figure PCTCN2022100563-appb-000073
Figure PCTCN2022100563-appb-000074
其中，Ar 1、Ar 2、Ar 3、X、R f1、R f2、R f3、k 1、k 2、k 3具有与式I中的相同的含义；Pd(PPh 3) 4代表四三苯基膦钯，Pd 2(dba) 3代表三(二苄基丙酮)二钯(0)，Sphos代表2-双环己基磷-2′，6′-二甲氧基联苯，IPr.HCl代表1，3-双(2，6-二异丙基苯基)氯化咪唑鎓，NaOBu-t代表叔丁醇钠，(t-Bu) 3P代表三叔丁基膦。
本申请式I化合物的制备包括上述方法，但不限于上述方法，本领域技术人员采用其他方法合成得到的式I化合物同样属于本申请的保护范围。
更具体地，本申请如下合成例示例性地提供了所述化合物的具体合成方法，如下合成例中所用溶剂和试剂，均可以从化工产品市场购买或定制。另外，本领域技术人员也可以通过其他公知方法合成。
以下合成例中的质谱表征数据通过英国Micromass公司制造的ZAB-HS型质谱仪测试得到。
合成例1：化合物P2
Figure PCTCN2022100563-appb-000075
在1000mL单口瓶中，加入20.0g的M1、20.7g的2-联苯硼酸、1.2g四三苯基膦钯Pd(PPh 3) 4、28.9g碳酸钾、300mL 1，4-二氧六环和100mL水，抽真空换氮气3次，反应升温至100℃反应5h。反应完毕，停止反应。冷却至室温，对反应液分液，有机相经过两次硅胶柱纯化，浓缩有机相，加入甲醇回流搅拌1h，抽滤得到淡黄色粉末M1-1，然后用乙酸乙酯重结晶得到纯品22.9g。
M1-1：m/z理论值：309；m/z实测值：310。
在1000mL单口瓶中，加入22.9g的M1-1、13.5g的苯硼酸、0.7g三(二苄基丙酮)二钯(0)Pd 2(dba) 3、0.6g的2-双环己基膦-2′，6′-二甲氧基联苯(Sphos)，31.4g无水磷酸钾，400mL 1，4-二氧六环和40mL水，抽真空换氮气3次，反应升温至100℃反应5h。反应完毕，停止反应。冷却至室温，对反应液分液，有机相经过两次硅胶柱纯化，浓缩有机相，加入甲醇回流搅拌1h，抽滤得到淡黄色粉末M1-2，然后用乙酸乙酯重结晶得到纯品16.9g。
M1-2：m/z理论值：351；m/z实测值：352。
在1000mL单口瓶中，加入16.9g的M1-2、2ml水合肼、0.5g钯碳(Pd/C)和300mL乙醇，抽真空换氮气3次，反应升温至90℃反应5h。反应完毕，停止反应。冷却至室温，对反应液分液，有机相经过两次硅胶柱纯化，浓缩有机相，加入甲醇回流搅拌1h，抽滤得到白色粉末M1-3，然后用乙酸乙酯重结晶得到纯品14.5g。
M1-3：m/z理论值：321；m/z实测值：322。
在1000mL单口瓶中，加入14.5g的M1-3、12.3g的2-溴-9，9-二甲基芴、0.4g Pd 2(dba) 3、0.4g的1，3-双(2，6-二异丙基苯基)氯化咪唑鎓(IPr.HCl)，13.0g叔丁醇钠NaOBu-t，300mL甲苯，抽真空换氮气3次，反应升温至90℃反应5h。反应完毕，停止反应。冷却至室温，对反应液分液，有机相经过两次硅胶柱纯化，浓缩有机相，加入甲醇回流搅拌1h，抽滤得到淡黄色粉末M1-4，然后用乙酸乙酯重结晶得到纯品17.1g。
M1-4：m/z理论值：513；m/z实测值：514。
在1000mL单口瓶中，加入17.1g的M1-4、7.7g的4-溴联苯、0.3g Pd 2(dba) 3、0.4mL三叔丁基膦(t-Bu) 3P，9.6g叔丁醇钠，300mL甲苯，抽真空换氮气3次，反应升温至110℃反应5h。反应完毕，停止反应。冷却至室温，对反应液分液，有机相经过两次硅胶柱纯化，浓缩有机相，加入甲醇回流搅拌1h，抽滤得到淡黄色粉末P2，然后乙酸乙酯重结晶三次的到纯品8.5g。
化合物P2：m/z理论值：665；m/z实测值：666。
合成例2-20，对比化合物CCP-3
合成例2-20的工艺路线与合成例1相同，区别在于原料不同，原料、目标产物及结果表征数据如表1所示。
表1
Figure PCTCN2022100563-appb-000076
Figure PCTCN2022100563-appb-000077
Figure PCTCN2022100563-appb-000078
Figure PCTCN2022100563-appb-000079
Figure PCTCN2022100563-appb-000080
实施例1
一种有机电致发光器件，包括依次设置的阳极(ITO)、空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层和阴极(Al)。
所述有机电致发光器件的制备方法如下：将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮/乙醇的混合溶剂中超声除油，在洁净环境下烘烤至完全除去水分，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；把上述带有阳极的玻璃基片置于真空腔内，抽真空至＜1×10 -5Pa，在上述阳极层膜上按先后顺序真空热蒸镀10nm的化合物HT-4∶HI-3(97/3，w/w)混合物作为空穴注入层，60nm的化合物HT-4作为空穴传输层，35nm的本申请提供的化合物P2作为电子阻挡层；40nm的化合物PH-61∶PH-3∶GPD-12(100∶100∶20，w/w)三元混合物作为发光层；5nm的ET-23作为空穴阻挡层，25nm的化合物ET-69∶ET-57(50/50，w/w)混合物作为电子传输层，1nm的LiF作为电子注入层，150nm的金属铝作为阴极；所有有机层和LiF的蒸镀总速率控制在0.1nm/s，金属电极的蒸镀速率控制在1nm/s。
实施例2-20、对比例1-5
一种有机电致发光器件，其与实施例1的区别仅在于，将电子阻挡层材料化合物P2替换为表2中的化合物。
对比例1-5的电子阻挡层材料的结构如下：
Figure PCTCN2022100563-appb-000081
Figure PCTCN2022100563-appb-000082
上述化合物CCP-1的来源可参考现有技术CN109485577A，CCP-2的来源可参考现有技术KR1020180104911A，CCP-3的制备方法如表1所示，CCP-4的来源可参考现有技术CN107017348A，CCP-5的来源可参考现有技术CN110903276A。
对上述实施例1-20和对比例1-5提供的有机电致发光器件进行如下性能测试：在同样亮度下，使用数字源表及亮度计测定有机电致发光器件的驱动电压和电流效率。具体而言，以每秒0.1V的速率提升电压，测定当有机电致发光器件的亮度达到10000cd/m 2时的电压即驱动电压，同时测出此时的电流密度；亮度与电流密度的比值即为电流效率；测试结果如表2所示。
表2
Figure PCTCN2022100563-appb-000083
Figure PCTCN2022100563-appb-000084
结合表2的数据可知，本申请提供的化合物用于有机电致发光器件，更有利于降低启亮电压、提高电流效率，使器件的驱动电压低至3.9-4.3V，电流效率达到64.9-69.4cd/A，是性能良好的绿光电子阻挡层材料。
对比例1的CCP-1与实施例11中的化合物P129的区别在于，N上连接的基团Ar 2为苯基，使CCP-1的平面性和芳香性较差，影响分子的结晶性和空间结构的致密性，导致对比例1的器件驱动电压高，电流效率低。对比例2的化合物CCP-2与实施例10的化合物P51的区别在于，苯环上芳胺N邻位的基团Ar 1为苯基，使CCP-2的结晶性较高，空间结构的致密性欠佳，导致对比例2的器件性能较差。CCP-3的分子结构中，芳胺N与芴基(二苯并五环结构)之间有苯环，会导致迁移率降低，且分子堆积致密性差，导致对比例3的器件性能较差；CCP-4的芳胺N邻位没有连接取代基，使分子的LUMO能级较深，降低了器件的发光性能；对比例5的电子阻挡层材料为CCP-5，其苯环上芳胺N邻位的基团Ar 1为硅杂芳基，导致CCP-5的迁移率低、分子的结晶性差，使有机电致发光器件的驱动电压较高、发光效率降低。
申请人声明，本申请通过上述实施例来说明本申请的一种化合物及其应用、一种有机电致发光器件，但本申请并不局限于上述实施例，即不意味着本申请必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。

Claims (13)

  1. 一种化合物，其特征在于，所述化合物具有如式I所示结构：
    Figure PCTCN2022100563-appb-100001
    其中，X选自O、S、CR 1R 2、NR 3或SiR 4R 5；
    Ar 1、Ar 2各自独立地选自取代的苯基、取代或未取代的C9-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；且当Ar 1包含
    Figure PCTCN2022100563-appb-100002
    时，Z 1选自O、S、CR 11R 12或NR 13；*代表基团的连接键；
    Ar 3选自取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；
    R 1、R 2、R 3、R 4、R 5、R 11、R 12、R 13各自独立地选自氢、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；R 1和R 2、R 4和R 5、R 11和R 12各自独立地不连接或通过化学键连接成环；
    R f1、R f2、R f3各自独立地选自卤素、氰基、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；
    Ar 1、Ar 2、Ar 3、R 1、R 2、R 3、R 4、R 5、R 11、R 12、R 13、R f1、R f2、R f3中所述取代的取代基各自独立地选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C2-C10杂环烷基、C1-C10烷氧基、C1-C10烷硫基、C6-C30芳基氨基、C3-C30杂芳基氨基、C6-C30芳基或C3-C30杂芳基中的至少一种；
    k 1、k 2各自独立地为0-3的整数；k 3为0-4的整数。
  2. 根据权利要求1所述的化合物，其特征在于，所述X为CR 1R 2、NR 3或SiR 4R 5，优选为CR 1R 2；
    优选地，所述R 1、R 2、R 3、R 4、R 5各自独立地选自取代或未取代的C1-C6直链或支链烷基、取代或未取代的C6-C18芳基、取代或未取代的C3-C18杂芳基中的任意一种；
    R 1和R 2不连接或通过化学键连接成环，R 4和R 5不连接或通过化学键连接成环；
    优选地，所述R 1、R 2、R 3、R 4、R 5各自独立地为甲基或苯基。
  3. 根据权利要求1所述的化合物，其特征在于，所述Ar 1选自取代的苯基、取代或未取代的C10-C20芳基、取代或未取代的C12-C30杂芳基中的任意一种；所述C12-C30杂芳基中的杂原子为O、S或N；
    优选地，所述Ar 1选自取代或未取代的如下基团中的任意一种：
    Figure PCTCN2022100563-appb-100003
    Figure PCTCN2022100563-appb-100004
    其中，*代表基团的连接键；
    R′选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10烷硫基、C6-C30芳基氨基、C3-C30杂芳基氨基、C6-C30芳基或C3-C30杂芳基；
    Z 1选自O、S、CR 11R 12或NR 13；
    R 11、R 12、R 13各自独立地选自氢、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；
    R 11和R 12不连接或通过化学键连接成环；
    n为1-5的整数。
  4. 根据权利要求1或3所述的化合物，其特征在于，所述Ar 1选自取代或未取代的如下基团中的任意一种：
    Figure PCTCN2022100563-appb-100005
    Figure PCTCN2022100563-appb-100006
    其中，*代表基团的连接键。
  5. 根据权利要求1所述的化合物，其特征在于，所述Ar 2选自取代的苯基、取代或未取代的C10-C20芳基、取代或未取代的C12-C30杂芳基中的任意一种；
    优选地，所述Ar 2选自取代或未取代的如下基团中的任意一种：
    Figure PCTCN2022100563-appb-100007
    其中，*代表基团的连接键；
    R″选自卤素、C1-C10直链或支链烷基、C3-C10环烷基、C1-C10烷氧基、C1-C10烷硫基、C6-C30芳基氨基、C3-C30杂芳基氨基、C6-C30芳基或C3-C30杂芳基；
    L选自单键、取代或未取代的C6-C30亚芳基、取代或未取代的C3-C30亚杂芳基中的任意一种；
    Z 2选自O、S、CR 21R 22、NR 23或SiR 24R 25；
    R 21、R 22、R 23、R 24、R 25各自独立地选自氢、取代或未取代的C1-C20直链或支链烷基、取代或未取代的C3-C20环烷基、取代或未取代的C2-C12烯基、取代或未取代的C2-C12炔基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基中的任意一种；
    R 21和R 22不连接或通过化学键连接成环，R 24和R 25不连接或通过化学键连接成环；
    m为1-5的整数。
  6. 根据权利要求5所述的化合物，其特征在于，所述L选自单键、取代或未取代的如下基团中的任意一种：
    Figure PCTCN2022100563-appb-100008
    其中，*代表基团的连接键。
  7. 根据权利要求1、5或6任一项所述的化合物，其特征在于，所述Ar 2选自取代或未取代的如下基团中的任意一种：
    Figure PCTCN2022100563-appb-100009
    Figure PCTCN2022100563-appb-100010
    其中，L选自
    Figure PCTCN2022100563-appb-100011
    Figure PCTCN2022100563-appb-100012
    中的任意一种；
    *代表基团的连接键。
  8. 根据权利要求1所述的化合物，其特征在于，所述Ar 3选自取代或未取代的如下基团中的任意一种：
    Figure PCTCN2022100563-appb-100013
    Figure PCTCN2022100563-appb-100014
    其中，*代表基团的连接键。
  9. 根据权利要求1所述的化合物，其特征在于，所述R f1、R f2、R f3各自独立地选自卤素、氰基、取代或未取代的C1-C6直链或支链烷基、取代或未取代的C3-C6环烷基、取代或未取代的C6-C18芳基、取代或未取代的C3-C18杂芳基中的任意一种；
    优选地，所述k 1、k 2、k 3均为0。
  10. 根据权利要求1所述的化合物，其特征在于，所述化合物具有如下P1-P590所示的结构中的任意一种：
    Figure PCTCN2022100563-appb-100015
    Figure PCTCN2022100563-appb-100016
    Figure PCTCN2022100563-appb-100017
    Figure PCTCN2022100563-appb-100018
    Figure PCTCN2022100563-appb-100019
    Figure PCTCN2022100563-appb-100020
    Figure PCTCN2022100563-appb-100021
    Figure PCTCN2022100563-appb-100022
    Figure PCTCN2022100563-appb-100023
    Figure PCTCN2022100563-appb-100024
    Figure PCTCN2022100563-appb-100025
    Figure PCTCN2022100563-appb-100026
    Figure PCTCN2022100563-appb-100027
    Figure PCTCN2022100563-appb-100028
    Figure PCTCN2022100563-appb-100029
    Figure PCTCN2022100563-appb-100030
    Figure PCTCN2022100563-appb-100031
    Figure PCTCN2022100563-appb-100032
    Figure PCTCN2022100563-appb-100033
    Figure PCTCN2022100563-appb-100034
    Figure PCTCN2022100563-appb-100035
    Figure PCTCN2022100563-appb-100036
    Figure PCTCN2022100563-appb-100037
    Figure PCTCN2022100563-appb-100038
    Figure PCTCN2022100563-appb-100039
    Figure PCTCN2022100563-appb-100040
    Figure PCTCN2022100563-appb-100041
    Figure PCTCN2022100563-appb-100042
    Figure PCTCN2022100563-appb-100043
    Figure PCTCN2022100563-appb-100044
    Figure PCTCN2022100563-appb-100045
    Figure PCTCN2022100563-appb-100046
    Figure PCTCN2022100563-appb-100047
    Figure PCTCN2022100563-appb-100048
    Figure PCTCN2022100563-appb-100049
    Figure PCTCN2022100563-appb-100050
    Figure PCTCN2022100563-appb-100051
    Figure PCTCN2022100563-appb-100052
    Figure PCTCN2022100563-appb-100053
  11. 根据权利要求10所述的化合物，其特征在于，所述化合物选自P2、P16、P20、P25、P28、P31、P38、P42、P44、P51、P129、P196、P221、P301、P341、P391、P441、P448、P461或P501中的至少一种。
  12. 一种如权利要求1-11中任一项所述的化合物的应用，其特征在于，所述化合物应用于有机电致发光器件、照明元件、有机薄膜晶体管、有机场效应晶体管、有机薄膜太阳能电池、信息标签、电子人工皮肤片材、片材型扫描器或电子纸；
    优选地，所述化合物在有机电致发光器件中作为电子阻挡材料和/或空穴传输材料。
  13. 一种有机电致发光器件，其特征在于，所述有机电致发光器件包括第一电极、第二电极以及设置于所述第一电极与第二电极之间的至少一个有机层；所述有机层中包括至少一种如权利要求1-11中任一项所述的化合物；
    优选地，所述有机层包括电子阻挡层，所述电子阻挡层中包括至少一种如权利要求1-11中任一项所述的化合物；
    优选地，所述有机层包括空穴传输层，所述空穴传输层中包括至少一种如权利要求1-11中任一项所述的化合物。
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