WO2025218079A1 - 含硼类化合物、电致发光器件及显示面板 - Google Patents

含硼类化合物、电致发光器件及显示面板

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Publication number
WO2025218079A1
WO2025218079A1 PCT/CN2024/113249 CN2024113249W WO2025218079A1 WO 2025218079 A1 WO2025218079 A1 WO 2025218079A1 CN 2024113249 W CN2024113249 W CN 2024113249W WO 2025218079 A1 WO2025218079 A1 WO 2025218079A1
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group
substituted
independently selected
unsubstituted
mmol
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French (fr)
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王雅洁
胡凤平
彭琴琴
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • 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 Table
    • 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
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • H10K85/658—Organoboranes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • C09K2211/1085—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with other heteroatoms

Definitions

  • the present application relates to the technical field of organic optoelectronic materials, and in particular to a boron-containing compound, an electroluminescent device, and a display panel.
  • OLEDs Organic light-emitting diodes
  • the core of OLEDs is the guest luminescent material, which has undergone three generations of evolution, from traditional fluorescent materials to phosphorescent materials and, more recently, thermally activated delayed fluorescence (TADF).
  • TADF thermally activated delayed fluorescence
  • the ratio of singlet excitons to triplet excitons is 1:3.
  • fluorescent materials triplet excitons are transition-forbidden, so fluorescent materials can only utilize the 25% singlet exciton ratio. Consequently, the efficiency of corresponding electroluminescent devices rarely exceeds 5%.
  • Phosphorescent materials exploit the spin-orbit coupling of heavy metal atoms and can emit light through radiative transitions of triplet excitons.
  • blue phosphorescent materials suffer from poor stability and cannot achieve deep blue emission.
  • Thermally activated delayed fluorescence materials are a class of materials with a small single-triplet energy level difference. They enable triplet excitons to reach the excited singlet state through a reverse intersystem crossing (RISC) process, and then emit light through radiative transition, thus realizing the utilization of triplet excitons.
  • RISC reverse intersystem crossing
  • the lifetime of most of these materials is short, and the half-width of the luminescence peak is wide, resulting in low color purity of the luminescence, which cannot meet the needs of industrial applications.
  • the embodiments of the present application provide a boron-containing compound, the general structural formula of the boron-containing compound is shown in formula (I):
  • Each is independently selected from a substituted or unsubstituted C 6 -C 60 aryl group, or a substituted or unsubstituted C 5 -C 60 heteroaryl group;
  • R 1 , R 2 , and R 3 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, -CN, -NO 2 , -CF 3 , -OH, -SH, -NH 2 , a C 1 -C 30 straight-chain hydrocarbon group, a C 3 -C 30 branched hydrocarbon group, a C 3 -C 30 cycloalkyl group, a C 1 -C 30 alkoxy group, a C 1 -C 30 alkylthio group, a C 6 -C 60 aryl group, a C 6 -C 60 aryl ether group, a C 5 -C 60 heteroaryl group, or a C 5 -C 60 heteroaryl ether group;
  • R is independently selected from a single bond, -CR 4 R 5 -, -CO-, -SiR 4 R 5 -, -NR 4 -, -POR 4 -, -O-, -S-, -Se-, -Te-, -SO-, or -SO 2 -;
  • R 4 and R 5 are independently selected from H, C 1 -C 30 alkyl, or C 6 -C 30 aryl;
  • G is selected from a nitrogen atom or a phosphino group
  • X, Y, and Z are each independently selected from a carbon atom or a nitrogen atom.
  • an embodiment of the present application further provides an electroluminescent device comprising an anode and a cathode, and a light-emitting layer located between the anode and the cathode, wherein the light-emitting layer comprises the above-mentioned boron-containing compound.
  • an embodiment of the present application further provides a display panel comprising the above-mentioned boron-containing compound or the above-mentioned electroluminescent device.
  • FIG1 is a schematic diagram of a film stack structure of an electroluminescent device provided in an embodiment of the present application.
  • the present application provides a boron-containing compound, an electroluminescent device and a display panel.
  • a boron-containing compound an electroluminescent device and a display panel.
  • the present application is further described in detail below. It is understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
  • substituted or unsubstituted means that the defined group may be substituted or unsubstituted.
  • R is selected from but not limited to: deuterium, tritium, cyano, isocyano, nitro, halogen, alkyl containing 1-20 carbon atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, Carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and the above groups may be further substituted by substituents acceptable in the art; it is understood that R' and R" in -
  • C 1-10 alkyl means an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
  • Constaining 3-10 ring atoms means containing 3, 4, 5, 6, 7, 8, 9 or 10 ring atoms.
  • the number of ring atoms in a benzene ring is 6, the number of ring atoms in a naphthalene ring is 10, and the number of ring atoms in a thienyl group is 5.
  • the number of ring atoms in methylbenzene is 6.
  • Aryl or “aromatic group” refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one ring is aromatic.
  • substituted or unsubstituted C6 - C60 aryl refers to an aromatic group containing 6 to 60 carbon atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and particularly preferably a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and the aromatic group is optionally further substituted.
  • Suitable examples include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylenyl, naphthacene, fluorenyl, perylene, acenaphthenyl, and derivatives thereof. It is understood that multiple aromatic groups may also be interrupted by short non-aromatic units (e.g.
  • non-H atoms such as C, N or O atoms
  • acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aromatic groups.
  • Heteroaryl or “heteroaromatic group” means that at least one carbon atom in an aryl group is replaced by a non-carbon atom (heteroatom), and the non-carbon atom (heteroatom) may be an oxygen, sulfur, selenium, tellurium, nitrogen atom, etc.
  • substituted or unsubstituted C5 - C60 heteroaryl means a heteroaryl group having 5 to 60 carbon atoms, preferably a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, more preferably a substituted or unsubstituted heteroaryl group having 5 to 18 carbon atoms, and particularly preferably a substituted or unsubstituted heteroaryl group having 5 to 14 carbon atoms, and the heteroaryl group may be optionally further substituted.
  • Suitable examples include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl , pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothiophenyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl,
  • alkyl may refer to a linear, branched and/or cyclic alkyl group.
  • the number of alkyl groups is 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6.
  • Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantyl, and the
  • the substituent abbreviations correspond to: n-normal, sec-secondary, i-iso, t-tertiary, o-ortho, m-meta, p-para, Me methyl, Et ethyl, Pr propyl, Bu butyl, Am n-pentyl, Hx hexyl, Cy cyclohexyl.
  • Halogen or "halogen atom” refers to F, Cl, Br or I.
  • alkoxy refers to a group of the structure "-O-alkyl", i.e., an alkyl group as defined above attached to another group via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to, methoxy (-O-CH 3 or -OMe), ethoxy (-O-CH 2 CH 3 or -OEt), and tert-butoxy (-OC(CH 3 ) 3 or -OtBu).
  • C 1 -C 30 alkyl refers to an unsubstituted C 1 -C 30 alkyl group
  • C 6 -C 60 aryl refers to an unsubstituted C 6 -C 60 aryl group.
  • the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.
  • Each is independently selected from a substituted or unsubstituted C 6 -C 60 aryl group or a substituted or unsubstituted C 6 -C 60 heteroaryl group.
  • R 1 , R 2 , and R 3 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, -CN, -NO 2 , -CF 3 , -OH, -SH, -NH 2 , a C 1 -C 30 straight-chain hydrocarbon group, a C 3 -C 30 branched hydrocarbon group, a C 3 -C 30 cycloalkyl group, a C 1 -C 30 alkoxy group, a C 1 -C 30 alkylthio group, a C 6 -C 60 aryl group, a C 6 -C 60 aryl ether group, a C 5 -C 60 heteroaryl group, or a C 5 -C 60 heteroaryl ether group.
  • R is independently selected from a single bond, -CR4R5- , -CO- , -SiR4R5- , -NR4-, -POR4- , -O- , -S-, -Se-, -Te-, -SO- or -SO2- ;
  • R4 and R5 are each independently selected from H, C1 - C30 alkyl or C6 - C30 aryl.
  • G is selected from a nitrogen atom or a phosphino group
  • X, Y, and Z are each independently selected from a carbon atom or a nitrogen atom.
  • boron-containing compounds have a large conjugated planar structure, which is prone to concentration quenching under electrical excitation, and there is a relatively serious efficiency roll-off problem in the device.
  • the boron-containing compounds provided in the embodiments of the present application introduce large sterically hindered heterocyclic aromatic hydrocarbon fragments, which make the molecules present a certain degree of distorted structure, effectively suppressing the concentration quenching effect, and the introduction of heteroatoms such as oxygen and sulfur is conducive to enhancing the spin-orbit coupling effect of the molecules, so that the molecules have a short delayed life, which is beneficial to improving the efficiency roll-off problem of the device.
  • the electroluminescent devices and display panels based on the boron-containing compounds have higher luminous efficiency and good device life.
  • the boron-containing compounds provided in the examples of the present application have a steady-state fluorescence spectrum in a toluene solution (10 -5 mol/L) with a wavelength range of 430-580 nm and a half-peak width of the spectrum less than 35 nm.
  • the transient luminescence in a solid-state film has delayed luminescence with a lifetime of 1 ⁇ s-100 ms.
  • the substituents of the above groups can form a ring with the above groups.
  • the design can make the molecules of the boron-containing compound asymmetrically substituted, and under the condition of electrical excitation, it is easy to obtain a better horizontal dipole orientation, thereby enhancing the light extraction efficiency of the device.
  • connection site “*” indicates the connection site
  • R 1 may be independently selected from H, substituted or unsubstituted C 6 -C 40 aryl, or substituted or unsubstituted C 5 -C 40 heteroaryl;
  • adjacent R 1 groups may or may not form a ring.
  • the general structural formula of the boron-containing compound is as shown in the following formula (I-1) or formula (I-2):
  • Each is independently selected from a substituted or unsubstituted C 6 -C 30 aryl group or a substituted or unsubstituted C 6 -C 30 heteroaryl group.
  • Each is independently selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted benzothiophene group, a substituted or unsubstituted benzofuran group, a substituted or unsubstituted indole group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted quinazoline group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzofuran group, a substituted or unsubstituted carbazole group or a substituted or unsubstituted triphenylamine group.
  • R 1 , R 2 and R 3 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, -CN, -NO 2 , -CF 3 , -OH, -SH, -NH 2 , a C 1 -C 30 straight chain hydrocarbon group, a C 3 -C 30 branched hydrocarbon group, a C 3 -C 30 cycloalkyl group, a C 1 -C 30 alkoxy group, a C 1 -C 30 alkylthio group, a C 6 -C 60 aryl group, a C 6 -C 60 aryl ether group, a C 5 -C 60 heteroaryl group, or a C 5 -C 60 heteroaryl ether group.
  • R is independently selected from a single bond, -CR4R5- , -CO- , -SiR4R5- , -NR4-, -POR4- , -O- , -S-, -Se-, -Te-, -SO- or -SO2- ;
  • R4 and R5 are each independently selected from H, C1 - C30 alkyl or C5 - C30 aryl.
  • MR-TADF multiple resonance thermally activated delayed fluorescence
  • the multiple resonance effect induces the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) to be located on different atoms, weakening the bonding/antibonding characteristics between atoms. This greatly reduces the change in electron density between atoms caused by the radiative transition from the lowest excited state to the ground state, thereby reducing stretching vibrations and effectively achieving narrow spectral emission (FWHM ⁇ 30nm).
  • FWHM ⁇ 30nm narrow spectral emission
  • the boron-containing compounds of the above formula (I-1) or (I-2) can easily obtain a better horizontal dipole orientation under electrical excitation conditions by designing asymmetrically substituted boron and nitrogen molecules, thereby enhancing the light extraction efficiency of the device.
  • the introduction of large sterically hindered heterocyclic aromatic hydrocarbon fragments makes the molecules present a certain twisted structure, which helps to suppress the concentration quenching effect.
  • the introduction of heteroatoms such as oxygen and sulfur is conducive to enhancing the spin-orbit coupling effect of the molecules, so that the molecules have a shorter delayed life, which helps to alleviate the efficiency roll-off problem of the device.
  • each is independently selected from a phenyl group which may be substituted or unsubstituted by a deuterium atom, -CH 3 , -C(CH 3 ) 3 , -CF 3 , -CN or -OCH 3 , a benzothiophene group, a biphenyl group, a naphthyl group, a quinazoline group, a carbazole group substituted by benzene or a dibenzofuran group.
  • a phenyl group which may be substituted or unsubstituted by a deuterium atom, -CH 3 , -C(CH 3 ) 3 , -CF 3 , -CN or -OCH 3 , a benzothiophene group, a biphenyl group, a naphthyl group, a quinazoline group, a carbazole group substituted by benzene or a dibenzofuran group.
  • each occurrence of R is independently selected from a single bond, -CR4R5- , -CO- , -SiR4R5- , -O-, -S- , -Se-, -Te-, -SO-, or -SO2- , and R4 and R5 are each independently selected from H, C1 - C10 alkyl, or C6 - C20 aryl.
  • the boron-containing compound is selected from one of the compounds represented by the following structural formula:
  • an embodiment of the present application further provides an electroluminescent device, comprising An anode, a cathode, and a light-emitting layer located between the anode and the cathode.
  • the light-emitting layer comprises the boron-containing compound in the above embodiment.
  • the light-emitting layer includes a host light-emitting material, a sensitizer and a guest light-emitting material, and the boron compound can be used as the guest light-emitting material.
  • the sensitizer may be at least one of a phosphorescent material and a thermally activated delayed fluorescent material.
  • the sensitizer is preferably a material having an emission peak in the range of 440-600 nm, phosphorescent emission, and a phosphorescence lifetime in the range of 1 ⁇ s to 100 ms.
  • the sensitizer has a HOMO energy level in the range of -6.0 eV to -5.0 eV, and a LUMO energy level in the range of -3.0 to -4.0 eV.
  • the boron compound is selected from a compound represented by a structural formula having a luminescence spectrum peak at 480-580 nm, a spectral half-width less than 60 nm, a HOMO energy level range of -6.0 eV to -5.0 eV, and a LUMO energy level range of -3.0 to -4.0 eV.
  • the electroluminescent device may further include a hole injection layer, a hole transport layer, and an electron blocking layer located between the anode and the light-emitting layer and sequentially stacked on the anode.
  • the electroluminescent device further includes a hole blocking layer, an electron transport layer, and an electron injection layer located between the light-emitting layer and the cathode and sequentially stacked on the light-emitting layer.
  • the electroluminescent device described in the present application can be selected from, but not limited to, organic light emitting diodes (OLEDs), organic photovoltaic cells, organic light emitting cells, organic field effect transistors, organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emission diodes, etc., with OLED being particularly preferred.
  • OLED organic light emitting diodes
  • the anode may include a conductive metal, a metal oxide, or a conductive polymer.
  • the anode can easily inject holes into the hole injection layer, the hole transport layer, or the light emitting layer.
  • examples of anode materials 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.
  • Other anode materials are known and can be readily selected and used by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, 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 the electroluminescent device according to the present application.
  • the cathode may comprise a conductive metal or metal oxide. electrons to the electron injection layer or electron transport layer or directly to the light emitting layer.
  • any material that can be used as a cathode in an OLED is suitable for use as the cathode material in the device of the present application.
  • cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloys, BaF2 /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO.
  • the cathode material can be deposited using any suitable technique, such as physical vapor deposition (PVD), including radio frequency magnetron sputtering, vacuum thermal evaporation, and electron beam (e-beam).
  • PVD physical vapor deposition
  • e-beam electron beam
  • the hole injection material, hole transport material, hole blocking material, electron blocking material, electron transport material and electron injection material used in the electroluminescent device of the present application are not particularly limited, and any compound can be used as long as the compound is commonly used as a hole injection material, hole transport material, electron blocking material, electron transport material and electron injection material.
  • the present application also relates to the application of the electroluminescent device according to the present application in various electronic devices, including but not limited to display devices, lighting devices, light sources, sensors, X-ray scintillator bio-imaging, etc.
  • display devices include but are not limited to mobile phones, car displays, AR, VR, laptop computers, televisions, etc.
  • the present application also provides a display panel comprising the aforementioned electroluminescent device.
  • the display panel may further comprise a pixel driving circuit for driving the electroluminescent device to emit light, the pixel driving circuit being electrically connected to the electroluminescent device.
  • the pixel driving circuit includes, but is not limited to, a thin-film transistor driving circuit.
  • K2CO3 potassium carbonate
  • DMSO dimethyl sulfoxide
  • Pd2 (dba) 3 tris(dibenzylideneacetone)dipalladium
  • S-Phos 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl
  • t-BuONa sodium tert-butoxide
  • tol toluene
  • DCM dichloromethane
  • CuI cuprous iodide
  • o-DCB o-dichlorobenzene
  • n-BuLi n-butyllithium
  • THF tetrahydrofuran
  • m-xylene m-xylene
  • the synthetic route of the target compound 1 of this embodiment is as follows:
  • target compound 1 In a 500 mL two-necked flask, intermediate 1-d (11.6 g, 12 mmol), palladium acetate (269 mg, 1.2 mmol), and silver oxide (5.57 g, 24 mmol) were added. The mixture was evacuated three times under an argon atmosphere, and pivalic acid (120 mL) was added. After reacting at 150°C for 6 h, anhydrous potassium carbonate (552 mg, 4 mmol) was added and the reaction was continued for 12 h. After the reaction temperature was cooled to room temperature, saturated aqueous sodium bicarbonate solution was added and stirred. The organic layer was extracted with DCM, concentrated, and purified by column chromatography to obtain the product target compound 1 (5 g, 5.4 mmol, yield 45%).
  • the synthetic route of target compound 2 in this example is as follows:
  • intermediate 2-b In a 500 mL two-necked flask, intermediate 2-a (6 g, 9 mmol) was added, and the flask was evacuated three times under an argon atmosphere. Anhydrous tetrahydrofuran (200 mL) was added, and then the apparatus was placed in a dry ice/acetone bath at -78 ° C and cooled for 15 min. n-Butyl lithium (45 mL, 18 mmol) was added. The n-hexane solution was added dropwise to the reaction flask using a syringe and allowed to react at -78°C for another 1 h.
  • intermediate 2-c Into a 500 mL two-necked flask were added intermediate 2-b (4.3 g, 5 mmol), 3,3-dimethyl-1-butene (3.2 mL, 25 mmol), and RhCl(PPh 3 ) 3 (46 mg, 0.05 mmol). The mixture was evacuated three times under an argon atmosphere, and anhydrous 1,4-dioxane (100 mL) was added. The mixture was reacted at 135° C. for 24 h. After the reaction was completed, the mixture was cooled to room temperature and extracted three times with DCM and water. The organic phases were combined and the solvent was removed. Intermediate 2-c (1.8 g, yield 84%) was obtained by column chromatography.
  • Intermediate 2-e In a 100 mL two-necked flask, intermediate 2-d (385 mg, 1 mmol), intermediate 2-c (860 mg, 1 mmol), and anhydrous potassium carbonate (276 mg, 2 mmol) were added. The mixture was evacuated three times under an argon atmosphere, and ultra-dry dimethyl sulfoxide (10 mL) was added. The mixture was then reacted at 150°C for 24 h. After the reaction mixture cooled to room temperature, it was extracted three times with DCM. The excess solvent was removed by rotary evaporation, and then purified by column chromatography to obtain intermediate 2-e (800 mg, 76% yield).
  • the synthetic route of target compound 3 in this example is as follows:
  • intermediate 3-c In a 500 mL two-necked flask, intermediate 3-b (9.8 g, 18 mmol), palladium acetate (410.4 mg, 1.8 mmol), and silver oxide (4.17 g, 18 mmol) were added. The flask was evacuated three times under an argon atmosphere, and pivalic acid (180 mL) was added. After the reaction was carried out at 150 ° C for 6 h, anhydrous Potassium carbonate (412 mg, 3 mmol) was added, and the reaction was continued for 12 h. After the reaction cooled to room temperature, saturated sodium bicarbonate aqueous solution was added and stirred until the pH of the solution system was neutral. The organic layer was then extracted with DCM, concentrated, and purified by column chromatography to obtain intermediate 3-c (4.87 g, 9 mmol, yield 50%).
  • Target Compound 3 To a 250 mL reaction flask, add intermediate 3-e (6.3 g, 7 mmol) and 140 mL of p-xylene. Add n-butyllithium in n-hexane (2.8 mL, 3.65 M, 7.14 mmol) dropwise at -40°C and stir for 1 h. Next, add boron tribromide (2.5 g, 10 mmol) dropwise at -78°C, stir at room temperature for 1 h, then add N,N-diisopropylethylamine (1.27 g, 10 mmol) dropwise at 0°C. Heat and stir at 150°C for 24 h. Cool to room temperature, extract the organic layer with DCM, concentrate, and purify by column chromatography to yield target compound 3 (2.33 g, 2.8 mmol, 40% yield).
  • the synthetic route of target compound 4 of this embodiment is as follows:
  • intermediate 4-b Under argon atmosphere, intermediate 4-a (1.2 g, 2 mmol) was added to a 100 mL two-necked flask, and 18 mL of anhydrous tetrahydrofuran was added and stirred. Then 20 mL (20 mmol) of methylmagnesium bromide was added dropwise. The mixture was reacted at 80°C for 12 h and then cooled to room temperature. Ethyl acetate and water were added for extraction, the organic phase was separated, and anhydrous sodium sulfate was added for drying. The organic phase obtained by filtration was free of solvent and purified by column chromatography to obtain intermediate 4-b (0.37 g, 0.6 mmol, yield: 30%).
  • Target Compound 4 Intermediate 4-e (500 mg, 0.5 mmol) and 10 mL of m-xylene were added to a 100 mL double-bottle flask. A solution of n-butyllithium in n-hexane (0.2 mL, 1 M, 0.51 mmol) was added dropwise at -40°C and stirred for 1 h. Boron tribromide (188 mg, 0.75 mmol) was then added dropwise at -78°C. The mixture was stirred at room temperature for 1 h. N,N-diisopropylethylamine (100 mg, 0.75 mmol) was then added dropwise at 0°C. The mixture was heated and stirred at 150°C for 24 h. After cooling to room temperature, the organic layer was extracted with DCM, concentrated, and purified by column chromatography to yield target compound 4 (202 mg, 0.2 mmol, 40% yield).
  • the synthetic route of target compound 5 of this embodiment is as follows:
  • Target Compound 5 To a 100 mL two-necked flask were added intermediate 5-d (480 mg, 0.5 mmol) and 10 mL of m-xylene. A solution of n-butyllithium in n-hexane (0.2 mL, 1 M, 0.51 mmol) was added dropwise at -40°C and stirred for 1 h. Boron tribromide (188 mg, 0.75 mmol) was then added dropwise at -78°C. The mixture was stirred at room temperature for 1 h. N,N-diisopropylethylamine (100 mg, 0.75 mmol) was then added dropwise at 0°C. The mixture was heated and stirred at 150°C for 24 h. After cooling to room temperature, the organic layer was extracted with DCM, concentrated, and purified by column chromatography to yield target compound 5 (204 mg, 0.23 mmol, 46% yield).
  • the synthetic route of target compound 6 in this example is as follows:
  • Target Compound 6 To a 500 mL reaction flask, add intermediate 6-e (22.1 g, 14 mmol) and 280 mL of p-xylene. Add n-butyllithium in n-hexane (5.6 mL, 7.3 mol/L, 14.28 mmol) dropwise at -40°C and stir for 1 h. Next, add boron tribromide (5 g, 20 mmol) dropwise at -78°C and stir at room temperature for 1 h. Then, add N,N-diisopropylethylamine (2.58 g, 20 mmol) dropwise at 0°C and heat with stirring at 150°C for 24 h. Cool to room temperature, extract the organic layer with DCM, concentrate, and purify by column chromatography to yield target compound 6 (6.4 g, 7.1 mmol, 45% yield).
  • the synthetic route of target compound 7 in this example is as follows:
  • intermediate 7-b In a 500 mL two-necked flask, intermediate 7-a (17.4 g, 21 mmol), palladium acetate (471 mg, 2.1 mmol), and silver oxide (9.75 g, 42 mmol) were added. The mixture was evacuated three times under an argon atmosphere, and pivalic acid (210 mL) was added. After reacting at 150°C for 6 h, anhydrous potassium carbonate (973 mg, 7 mmol) was added and the reaction was continued for 12 h. After the reaction temperature was cooled to room temperature, saturated aqueous sodium bicarbonate solution was added and stirred. The organic layer was extracted with DCM, concentrated, and purified by column chromatography to obtain intermediate 7-b (8.25 g, 10 mmol, yield 48%).
  • Target Compound 7 To a 500 mL two-necked flask, intermediate 7-d (9.17 g, 7 mmol) and 140 mL of p-xylene were added dropwise. A solution of n-butyllithium in n-hexane (2.8 mL, 3.6 M, 7.14 mmol) was added dropwise at -40°C and stirred for 1 h. Boron tribromide (2.5 g, 10 mmol) was then added dropwise at -78°C. The mixture was stirred at room temperature for 1 h. N,N-diisopropylethylamine (1.27 g, 10 mmol) was then added dropwise at 0°C. The mixture was heated and stirred at 150°C for 24 h. After cooling to room temperature, the organic layer was extracted with DCM, concentrated, and purified by column chromatography to yield target compound 7 (3.7 g, 3 mmol, 43% yield).
  • the synthetic route of target compound 8 in this example is as follows:
  • target compound 8 Into a 200 mL two-necked flask were added intermediate 8-d (4.36 g, 5 mmol), palladium acetate (112 mg, 0.5 mmol), and silver oxide (2.31 g, 10 mmol). The mixture was evacuated three times under an argon atmosphere, and pivalic acid (50 mL) was added. After reacting at 150°C for 6 h, anhydrous potassium carbonate (135 mg, 1 mmol) was added and the reaction was continued for 12 h. After the reaction temperature was cooled to room temperature, saturated aqueous sodium bicarbonate solution was added and stirred. The organic layer was extracted with DCM, concentrated, and purified by column chromatography to obtain the target compound 8 (1.8 g, 2.1 mmol, 42% yield).
  • the synthetic route of target compound 9 in this example is as follows:
  • intermediate 9-b In a 1000 mL reaction flask, intermediate 9-a (23.5 g, 45 mmol), 5-phenyl-5,11-dihydroindole[3,2-B]carbazole (16.6 g, 50 mmol), palladium acetate (600 mg, 2.5 mmol), tri-tert-butylphosphine tetrafluoroborate (1.41 g, 5 mmol), sodium tert-butoxide (5.76 g, The reaction mixture was purged three times under an argon atmosphere, and anhydrous toluene (400 mL) was added. The mixture was then reacted at 110°C for 36 h. After the reaction cooled to room temperature, the mixture was extracted three times with DCM. The excess solvent was removed by rotary evaporation, and the mixture was purified by column chromatography to obtain intermediate 9-b (23.7 g, 68% yield).
  • intermediate 9-c In a 500 mL two-necked flask, intermediate 9-b (23.2 g, 30 mmol), palladium acetate (672 mg, 3 mmol), and silver oxide (13.9 g, 60 mmol) were added. The mixture was evacuated three times under an argon atmosphere, and pivalic acid (360 mL) was added. After reacting at 150°C for 6 h, anhydrous potassium carbonate (1.38 g, 10 mmol) was added and the reaction was continued for 12 h. After the reaction temperature was cooled to room temperature, saturated aqueous sodium bicarbonate solution was added and stirred. The organic layer was extracted with DCM, concentrated, and purified by column chromatography to obtain intermediate 9-c (9.9 g, 12.9 mmol, yield 43%).
  • Target Compound 9 To a 500 mL reaction flask, add intermediate 9-e (10.8 g, 9 mol) and 90 mL of p-xylene. Add n-butyllithium in n-hexane (3.7 mL, 9.18 mmol) dropwise at -40°C and stir for 1 h. Next, add boron tribromide (2.7 g, 10.8 mmol) dropwise at -78°C, stir at room temperature for 1 h, then add N,N-diisopropylethylamine (1.39 g, 10.8 mmol) dropwise at 0°C. Heat and stir at 150°C for 24 h. Cool to room temperature, extract the organic layer with DCM, concentrate, and purify by column chromatography to yield target compound 9 (3.9 g, 3.5 mmol, 38% yield).
  • the synthetic route of the target compound 10 of this embodiment is as follows:
  • reaction was then carried out at 110°C for 36 h. After the reaction mixture cooled to room temperature, it was extracted three times with DCM. The excess solvent was removed by rotary evaporation, and then purified by column chromatography to obtain intermediate 10-b (10.3 g, 13 mmol, Yield 65%).
  • intermediate 10-c In a 500 mL two-necked flask, intermediate 10-b (8 g, 10 mmol), palladium acetate (225 mg, 1 mmol), and silver oxide (4.64 g, 20 mmol) were added. The mixture was evacuated three times under an argon atmosphere, and pivalic acid (100 mL) was added. After reacting at 150°C for 6 h, anhydrous potassium carbonate (690 mg, 5 mmol) was added and the reaction was continued for 12 h. After the reaction temperature was cooled to room temperature, saturated aqueous sodium bicarbonate solution was added and stirred. The organic layer was extracted with DCM, concentrated, and purified by column chromatography to obtain intermediate 10-c (3.72 g, 4.7 mmol, yield 47%).
  • Target Compound 10 To a 500 mL reaction flask, add intermediate 10-e (10.8 g, 3 mol) and 30 mL of p-xylene. Add n-butyllithium in n-hexane (1.22 mL, 3.06 mmol) dropwise at -40°C and stir for 1 h. Next, add boron tribromide (0.9 g, 3.6 mmol) dropwise at -78°C, stir at room temperature for 1 h, then add N,N-diisopropylethylamine (465 mg, 3.6 mmol) dropwise at 0°C. Heat and stir at 150°C for 24 h. Cool to room temperature, extract the organic layer with DCM, concentrate, and purify by column chromatography to yield target compound 10 (1.08 g, 1 mmol, 35% yield).
  • MS mass spectrometry
  • EA elemental analysis
  • FIG1 A schematic diagram of the film stack structure of the electroluminescent device is shown in FIG1 , wherein: 1—glass and conductive glass (ITO anode) substrate layer; 2—hole injection layer (HATCN, 10 nm); 3—hole transport layer (TAPC, 30 nm); 4—electron blocking layer (TCTA, 15 nm); 5—luminescent layer (20 nm); 6—hole blocking layer (DBFPO, 20 nm); 7—electron transport layer (ANT-BIZ, 30 nm); 8—electron injection layer (LiQ, 1 nm); 9—cathode (Al, 100 nm).
  • ITO anode glass and conductive glass
  • device embodiments 1-20 and device comparative example 1 are identical in device structure and manufacturing method except that the materials of the light-emitting layers are different.
  • the light-emitting layer of the device comparative example 1 compound A and the main light-emitting material mCBP, the evaporation ratio is 4:196.
  • the light-emitting layer of the device comparative example 2 compound A, photosensitizer Ir(ppy) 3 and main light-emitting material mCBP, the evaporation ratio is 2:20:178.
  • the light-emitting layer of device example 1 is different from device comparative example 1 in that compound A is replaced by compound 1 synthesized in example 1.
  • the light-emitting layer of device example 2 is different from device comparative example 1 in that compound A is replaced by compound 2 synthesized in example 2.
  • the light-emitting layer of device example 3 is different from device comparative example 1 in that compound A is replaced by compound 3 synthesized in example 3.
  • the light-emitting layer of device example 4 is different from device comparative example 1 in that compound A is replaced by compound 4 synthesized in example 4.
  • the light-emitting layer of device example 5 is different from device comparative example 1 in that compound A is replaced by compound 5 synthesized in example 5.
  • the light-emitting layer of device example 6 is different from device comparative example 1 in that compound A is replaced by compound 6 synthesized in example 6.
  • the light-emitting layer of device embodiment 7 is different from that of device comparative example 1 in that compound A is replaced with This is compound 7 synthesized in Example 7.
  • the light-emitting layer of device example 8 is different from device comparative example 1 in that compound A is replaced by compound 8 synthesized in example 8.
  • the light-emitting layer of device example 9 is different from device comparative example 1 in that compound A is replaced by compound 9 synthesized in example 9.
  • the light-emitting layer of device example 10 is different from device comparative example 1 in that compound A is replaced by compound 10 synthesized in example 10.
  • the light-emitting layer of device example 11 is different from device comparative example 2 in that compound A is replaced by compound 1 synthesized in example 1.
  • the light-emitting layer of device example 12 is different from device comparative example 2 in that compound A is replaced by compound 2 synthesized in example 2.
  • the light-emitting layer of device example 13 is different from device comparative example 2 in that compound A is replaced by compound 3 synthesized in example 3.
  • the light-emitting layer of device example 14 is different from device comparative example 2 in that compound A is replaced by compound 4 synthesized in example 4.
  • the light-emitting layer of device example 15 is different from device comparative example 2 in that compound A is replaced by compound 5 synthesized in example 5.
  • the light-emitting layer of device example 16 is different from device comparative example 2 in that compound A is replaced by compound 6 synthesized in example 6.
  • the light-emitting layer of device example 17 is different from device comparative example 2 in that compound A is replaced by compound 7 synthesized in example 7.
  • the light-emitting layer of device example 18 is different from device comparative example 2 in that compound A is replaced by compound 8 synthesized in example 8.
  • the light-emitting layer of device example 19 is different from device comparative example 1 in that compound A is replaced by compound 9 synthesized in example 9.
  • the light-emitting layer of device example 20 is different from device comparative example 2 in that compound A is replaced by compound 10 synthesized in example 10.
  • the electroluminescent device can be manufactured according to methods known in the art, for example, according to the method disclosed in the reference (Adv. Mater. 2003, 15, 277.).
  • the specific method is: under high vacuum conditions, The hole injection layer, hole transport layer, electron blocking layer, luminescent layer, hole blocking layer, electron transport layer, electron injection layer, and cathode were sequentially deposited on a cleaned conductive glass (ITO) substrate.
  • ITO conductive glass
  • This method produced the device shown in Figure 1.
  • the luminescence characteristics of the prepared device were recorded at a current density of 10 mA/ cm2 , as shown in Table 2. Where Voltage is the operating voltage of the device, and CE is the current efficiency. Higher current efficiency indicates greater carrier utilization and higher luminescence efficiency.
  • the electroluminescent devices prepared in Device Examples 1-10 provided in the Examples of the present application have lower operating voltages, higher luminous efficiencies, and longer service lives. This may be because the compounds provided in the Examples of the present application, by introducing a heterocyclic aromatic hydrocarbon fragment with greater steric hindrance, cause the molecule to exhibit a certain degree of distorted structure, which can effectively suppress the concentration quenching effect, and by introducing heteroatoms such as oxygen and sulfur, it is beneficial to enhance the spin-orbit coupling effect of the molecule, thereby giving the molecule a short delayed life, thereby improving the luminous efficiency and service life of the device as a whole.
  • the electroluminescent devices prepared by device embodiments 11-20 can further reduce the operating voltage, increase the luminescence and extend the service life.
  • the possible reason is that by introducing phosphorescent materials into the light-emitting layer and combining them with the compounds provided in the embodiments of the present application, the efficient phosphorescent materials can capture triplet excitons in the electroluminescent device and transfer energy to the fluorescent molecules (compounds provided in the present application) through energy transfer, so that the fluorescent molecules emit light. While maintaining the narrow spectrum of the fluorescent molecules, efficient utilization of triplet excitons is achieved, thereby realizing an electroluminescent device with high efficiency, high color purity and high stability.

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Abstract

公开一种含硼类化合物、电致发光器件及显示面板，含硼类化合物的结构通式为(I)，式(II) 、(III)至式(IV)选自芳基或杂芳基，R1至R3选自氢、氘、卤素、-CN、-NO2、-CF3、-OH、-SH、-NH2、直链烃基、支链烃基、环烷基、烷氧基、烷硫基、芳基、芳醚基、杂芳基或杂芳醚基，R选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-，G选自氮原子或膦氧基，X、Y、Z选自碳或氮。

Description

含硼类化合物、电致发光器件及显示面板
本申请要求于2024年04月19日提交的申请号为202410480910.8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
本申请涉及有机光电材料技术领域，尤其涉及一种含硼类化合物、电致发光器件及显示面板。
背景技术
有机电致发光二极管(organic light-emitting diode，OLED)凭借自发光、对比度高、视角广、发光效率高、相应速度快、轻薄、可折叠等优势，在柔性显示和固态照明领域具有广阔的应用前景。OLED的核心是客体发光材料。客体发光材料从最初的传统荧光材料，发展到磷光材料，再到近年来的热活化延迟荧光材料(thermally activated delayed fluorescence，TADF)，历经三代更迭。在电致激发下，单重态激子与三重态激子的比例为1:3，在荧光材料中，三重态激子是跃迁禁阻的，因此荧光材料只能利用占比为25％的单重态激子，导致相应的电致发光器件的效率很难突破5％。磷光材料可利用重金属原子的自旋轨道耦合作用，可利用三重态激子辐射跃迁发光。但蓝光磷光材料的稳定性较差，且无法实现深蓝光的发射。热活化延迟荧光材料是一类具有较小的单三重态能级差的材料，使三重态激子通过反向系间窜跃(reverse intersystem crossing，RISC)过程到达激发单重态，进而辐射跃迁发光，实现三重态激子的利用，但此类材料的寿命大多较短，并且发光峰的半峰宽较宽导致发光的色纯度不高，无法满足工业应用的需求。
基于上述缺陷，高发光效率、高发光色纯度以及长发光寿命的发光材料有待于开发。
发明内容
现有的发光材料存在发光效率、发光色纯度以及寿命有待于提高的问题。
第一方面，本申请实施例提供一种含硼类化合物，所述含硼类化合物的结构通式如式(I)所示：
其中，各自独立地选自取代或未取代的C6-C60的芳基、或取代或未取代的C5-C60的杂芳基；
R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5自独立地选自H、C1-C30的烷基、或C6-C30的芳基；
G选自氮原子或膦氧基；
X、Y、Z各自独立地选自碳原子或氮原子。
第二方面，本申请实施例还提供一种电致发光器件，包括阳极和阴极，以及位于所述阳极和所述阴极之间的发光层，所述发光层包括上述含硼类化合物。
第三方面，本申请实施例还提供一种显示面板，包括上述含硼类化合物或上述电致发光器件。
附图说明
下面结合附图，通过对本申请的具体实施方式详细描述，将使本申请的技术方案及其它有益效果显而易见。
图1为本申请实施例提供的电致发光器件的膜层叠构示意图。
本发明的实施方式
本申请提供一种含硼类化合物、电致发光器件及显示面板。为使本申请的目的、技术方案及效果更加清楚、明确，以下对本申请进一步详细说明。应当 理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
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申请的技术领域的技术人员通常理解的含义相同。本文中在本申请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，不是旨在于限制本申请。在本申请中，“取代”表示被取代基中的氢原子被取代基所取代。
在本申请中，“取代或未取代”表示所定义的基团可以被取代，也可以不被取代。当所定义的基团为被取代时，应理解为所定义的基团可以被一个或多个取代基R取代，所述R选自但不限于：氘、氚、氰基、异氰基、硝基、卤素、含有1-20个碳原子的烷基、含有3-20个环原子的杂环基、含有6-20个环原子的芳香基团、含有5-20个环原子的杂芳香基团、-NR’R”、硅烷基、羰基、烷氧基羰基、芳氧基羰基、氨基甲酰基、卤甲酰基、甲酰基、异氰酸酯基、硫氰酸酯基、异硫氰酸酯基、羟基、三氟甲基，且上述基团也可以进一步被本领域可接受取代基取代；可理解的，-NR’R”中R’和R”分别独立选自但不限于：H、氘、氚、氰基、异氰基、硝基或卤素、含有1-10个碳原子的烷基、含有3-20个环原子的杂环基、含有6-20个环原子的芳香基团、含有5-20个环原子的杂芳香基团。优选地，R选自但不限于：氘、氚、氰基、卤素、金刚烷、甲基、甲氧基、三氟甲基、乙基、丙基、异丙基、丁基、叔丁基、异丁基、仲丁基、新戊基、正戊基、异戊基、辛基、庚基、正癸基、1-甲基戊基、2-甲基戊基、3-甲基戊基、1-丁基戊基、环丙基、环丁基、环戊基、环己基,4-甲基环己基、4,4-二甲基环己基、金刚烷基和环庚基、苯基、二联苯基、三联苯基、萘基、蒽基、芘基、菲基、吡啶基、嘧啶基、吡嗪基、喹啉基、异喹啉基、萘啶基、恶唑基、苯并惡唑基、咪唑基、苯并咪唑基、呋喃基、噻吩基、二苯并呋喃基、二苯并噻吩基、咔唑基、N-苯基咔唑基、9,9-4甲基芴基、9,9-二苯基芴基、螺芴基。
本申请中，用数值范围描述的原子数量，包括数值范围的两个整数端点，还包括两个端点中的每一个整数。举例如，“C1-10的烷基”表示具有1、2、3、4、5、6、7、8、9或10个碳原子的烷基。“含有3-10个环原子”表示含有3、4、5、6、7、8、9或10个环原子。
在本申请中，“环原子数”表示原子键合成环状而得到的结构化合物(例如，单环化合物、稠环化合物、交联化合物、碳环化合物、杂环化合物)的构成该 环自身的原子之中的原子数。该环被取代基所取代时，取代基所包含的原子不包括在成环原子内。关于以下所述的“环原子数”，在没有特别说明的条件下也是同样的。例如，苯环的环原子数为6，萘环的环原子数为10，噻吩基的环原子数为5。又例如，甲基苯的环原子数为6。
“芳基”或“芳香基团”是指在芳香环化合物的基础上除去一个氢原子衍生的芳族烃基，可以为单环芳基、或稠环芳基、或多环芳基，对于多环的环种，至少一个是芳族环系。例如，“取代或未取代的C6-C60的芳基”是指包含6至60个碳原子的芳基，优选取代或未取代的具有6至30个碳原子的芳基，更优选取代或未取代的具有6至18个碳原子的芳基，特别优选取代或未取代的具有6至14个碳原子的芳基，且芳基上任选进一步被取代；合适的实例包括但不限于：苯基、联苯基、三联苯基、萘基、蒽基、菲基、荧蒽基、三亚苯基、芘基、苝基、并四苯基、芴基、二萘嵌苯基、苊基及其衍生物。可以理解地，多个芳基也可以被短的非芳族单元间断(例如<10％的非H原子，比如C、N或O原子)，具体如苊、芴，或者9,9-二芳基芴、三芳胺、二芳基醚体系也应该包含在芳基的定义中。
“杂芳基”或“杂芳香基团”是指在芳基的基础上至少一个碳原子被非碳原子(杂原子)所替代，非碳原子(杂原子)可以为氧、硫、硒、碲、氮原子等。例如，“取代或未取代的C5-C60的杂芳基”是指具有5至60个碳原子的杂芳基，优选取代或未取代的具有5至30个碳原子的杂芳基，更优选取代或未取代的具有5至18个碳原子的杂芳基，特别优选取代或未取代的具有5至14个碳原子的杂芳基，且杂芳基可任选进一步被取代，合适的实例包括但不限于：噻吩基、呋喃基、吡咯基、咪唑基、二唑基、三唑基、咪唑基、吡啶基、联吡啶基、嘧啶基、三嗪基、吖啶基、哒嗪基、吡嗪基、喹啉基、异喹啉基、喹唑啉基、喹喔啉基、酞嗪基、吡啶并嘧啶基、吡啶并吡嗪基、苯并噻吩基、苯并呋喃基、吲哚基、吡咯并咪唑基、吡咯并吡咯基、噻吩并吡咯基、噻吩并噻吩基、呋喃并吡咯基、呋喃并呋喃基、噻吩并呋喃基、苯并异噁唑基、苯并异噻唑基、苯并咪唑基、邻二氮萘基、菲啶基、伯啶基、喹唑啉酮基、二苯并噻吩基、二苯并呋喃基、咔唑基及其衍生物。
在本申请中，“烷基”可以表示直链、支链和/或环状烷基。烷基的碳数可 以为1至50、1至30、1至20、1至10或1至6。烷基的非限制性实例包括甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、异丁基、2-乙基丁基、3,3-二甲基丁基、正戊基、异戊基、新戊基、叔戊基、环戊基、1-甲基戊基、3-甲基戊基、2-乙基戊基、4-甲基-2-戊基、正己基、1-甲基己基、2-乙基己基、2-丁基己基、环己基、金刚烷基等。
在本申请中，取代基缩写对应为：n-正，sec-仲，i-异，t-叔，o-邻，m-间，p-对，Me甲基，Et乙基，Pr丙基，Bu丁基，Am正戊基，Hx己基，Cy环己基。
“卤素”或“卤素原子”是指F、Cl、Br或I。
术语“烷氧基”是指结构为“-O-烷基”的基团，即如上所定义的烷基经由氧原子连接至其它基团。包含该术语的短语，合适的实例包括但不限于：甲氧基(-O-CH3或-OMe)、乙氧基(-O-CH2CH3或-OEt)和叔丁氧基(-O-C(CH3)3或-OtBu)。
本申请中，“进一步”、“更进一步”、“特别”等用于描述目的，表示内容上的差异，但并不应理解为对本发明保护范围的限制。
本申请中，“可选地”、“可选的”、“可选”，指可有可无，也即指选自“有”或“无”两种并列方案中的任一种。如果一个技术方案中出现多处“可选”，如无特别说明，且无矛盾之处或相互制约关系，则每项“可选”各自独立。
本申请中，在描述各个基团时，若未强调取代情况，则默认为该基团是未取代的。如“C1-C30的烷基”指的是未取代的C1-C30的烷基，“C6-C60的芳基”指的是未取代的C6-C60的芳基。
本申请中，以开放式描述的技术特征中，包括所列举特征组成的封闭式技术方案，也包括包含所列举特征的开放式技术方案。
本申请实施例提供的含硼类化合物的结构通式如下式(1)所示：
其中，选自取代或未取代的C6-C60的芳基、或取代或未取代的C5-C60 的杂芳基。
各自独立地选自取代或未取代的C6-C60的芳基、或取代或未取代的C6-C60的杂芳基。
R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基。
R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5各自独立地选自H、C1-C30的烷基或C6-C30的芳基。
G选自氮原子或膦氧基，X、Y、Z各自独立地选自碳原子或氮原子。
现有的含硼类化合物具有较大的共轭平面结构，在电致激发情况下容易发生浓度猝灭，器件方面存在着比较严重的效率滚降问题。而本申请实施例提供的含硼类化合物，引入大位阻的杂环芳烃片段，使得分子呈现一定程度的扭曲结构，有效地抑制了浓度淬灭效应，且引入氧硫等杂原子，有利于增强分子的自旋轨道耦合效应，使得分子有短的延迟寿命，有利改善器件的效率滚降问题。基于该含硼类化合物的电致发光器件及显示面板具有更高的发光效率和良好的器件寿命。
本申请实施例提供的含硼类化合物在甲苯溶液(10-5mol/L)中的稳态荧光光谱波长范围为430-580nm，光谱的半峰宽小于35nm；在固态薄膜下的瞬态发光具有延迟发光，寿命为1us-100ms。
在本申请的一些实施例中，选自取代或未取代的苯基、取代或未取代的萘基、或取代或未取代的蒽基。当上述基团被取代时，上述基团的取代基可与上述基团相互成环。通过上述基团的设计，可使得该含硼类化合物的分子呈不对称取代，在电致激发条件下，易获得较好的水平偶极取向，从而增强器件的出光效率。
具体地，可选自以下结构中的任意一种：
其中，“*”表示连接位点；
R1每次出现时，可独立地选自H、取代或未取代的C6-C40的芳基、或取代或未取代的C5-C40的杂芳基；
在一些实施例中，相邻的R1之间可成环，也可不成环。
在本申请的一些实施例中，所述含硼类化合物的结构通式如下式(I-1)或式(I-2)所示：
至各自独立地选自取代或未取代的C6-C30的芳基、或取代或未取代的C6-C30的杂芳基。
可选地，至各自独立地选自取代或未取代的苯基、取代或未取代的吡啶基团、取代或未取代的苯并噻吩基团、取代或未取代的苯并呋喃基团、取代或未取代的吲哚基团、取代或未取代的萘基、取代或未取代的喹唑啉基团、取代或未取代的联苯基团、取代或未取代的二苯并呋喃基团、取代或未取代的咔唑基团或取代或未取代的三苯胺基团。
R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、 C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基。
R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5各自独立地选自H、C1-C30的烷基或C5-C30的芳基。
通过将缺电子的B元素与富电子的N元素交替排列，利用B和N原子相反的共振效应构建多重共振热活化延迟荧光(MR-TADF)，通过多重共振效应诱导最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)定位在不同的原子上，使得原子之间的成键/反键特性减弱，在很大程度上减小了最低激发态至基态辐射跃迁产生的原子之间的电子密度的变化，从而减小了伸缩震动，有效地实现了窄光谱发射(FWHM＜30nm)。同时分子的热活化延迟荧光性质也保证了材料的高发光效率。
具有上述式(I-1)或(I-2)的含硼类化合物，通过设计不对称取代的硼氮分子，在电致激发条件下易获得较好的水平偶极取向，可增强器件出光效率；并且在影响光谱半峰宽的前提下，引入大位阻的杂环芳烃片段，使得分子呈现一定的扭曲结构，有助于抑制浓度淬灭效应；并且氧硫等杂原子的引入，有利于增强分子的自旋轨道耦合效应，使得分子具有较短的延迟寿命，有助于缓解器件的效率滚降问题。
可选地，在一些实施例中，至各自独立地选自被氘原子、-CH3、-C(CH3)3、-CF3、-CN或-OCH3取代或未取代的苯基、苯并噻吩基团、联苯基团、萘基、喹唑啉基团、被苯取代的咔唑基团或二苯并呋喃基团。
可选地，在一些实施例中，R1、R2、R3各自独立地选自氢原子、CN、CF3或-OCH3。
可选地，在一些实施例中，R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-，R4和R5各自独立地选自H、C1-C10的烷基或C6-C20的芳基。
具体地，在一些实施例中，所述含硼类化合物选自如下结构式所示的化合物中的一种：


基于上述含硼类化合物，本申请的实施例还提供一种电致发光器件，包括 阳极和阴极、以及位于阳极和阴极之间的发光层。所述发光层包括上述实施例中的含硼类化合物。
所述发光层包括主体发光材料、敏化剂和客体发光材料，所述硼类化合物可作为客体发光材料使用。
在一些实施例中，所述敏化剂可选用磷光材料和热活化延迟荧光材料中的至少一种。进一步地，所述敏化剂优先选择发射峰值位于440-600nm、具有磷光发射且磷光寿命在1us-100ms的材料。所述敏化剂的HOMO能级范围为-6.0eV至-5.0eV,其LUMO能级范围为-3.0至-4.0eV。
进一步地，在一些实施例中，所述硼类化合物选用发光光谱峰值位于480-580nm、光谱半峰宽小于60nm、HOMO能级范围为-6.0eV至-5.0eV、LUMO能级范围为-3.0～-4.0eV的结构式所示的化合物。
在一些实施例中，所述电致发光器件还可包括位于所述阳极和所述发光层之间，并依次层叠于所述阳极上的空穴注入层、空穴传输层以及电子阻挡层
在一些实施例中，所述电致发光器件还包括位于所述发光层与所述阴极之间，并依次层叠于所述发光层上的空穴阻挡层、电子传输层、电子注入层。
按照本申请所述的电致发光器件可选于，但不限于，有机发光二极管(OLED)、有机光伏电池、有机发光电池、有机场效应管、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等，特别优选为OLED。
在本申请的实施例中，阳极可包括导电金属、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、空穴传输层或发光层中。
在一些实施例中，阳极材料的举例包括但不限于：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。
在一些实施例中，阳极是图案结构化的。图案化的ITO导电基片可在市场上买到，并且可以用来制备根据本申请的电致发光器件。
本发明中，阴极可包括一导电金属或金属氧化物。阴极可以容易地注入电 子到电子注入层或电子传输层或直接到发光层中。
原则上，所有可用作OLED的阴极的材料都可能作为本申请器件的阴极材料。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。
用于本申请电致发光器件中的空穴注入材料、空穴传输材料、空穴阻挡材料、电子阻挡材料、电子传输材料、电子注入材料不受特别的限制，并且可以使用任何化合物，只要该化合物通常用作空穴注入材料、空穴传输材料、电子阻挡材料、电子传输材料、电子注入材料。
本申请还涉及按照本申请的电致发光器件在各种电子设备中的应用，包含但不限于显示设备，照明设备，光源，传感器、X射线闪烁体生物成像等等。显示设备举例来说包括但不限于移动手机、车载显示屏、AR、VR、笔记本电脑、电视等。
本申请还提供一种显示面板，所述显示面板包括上述电致发光器件。所述显示面板还可包括驱动上述电致发光器件发光的像素驱动电路，所述像素驱动电路与所述电致发光器件电连接。所述像素驱动电路包括但不限于为薄膜晶体管驱动电路。
具体实施例
下面通过具体实施例来对本发明进行具体说明，以下实施例仅是本发明的部分实施例，不是对本发明的限定。以下实施例中所用的原料，如无特别说明，均为市售产品。其中，K2CO3：碳酸钾；DMSO：二甲亚砜；Pd2(dba)3：三(二亚苄基丙酮)二钯；S-Phos：2-二环己基膦-2’,6’-二甲氧基-1,1’-联苯；t-BuONa：叔丁醇钠；tol：甲苯；DCM：二氯甲烷；CuI：碘化亚铜；o-DCB：邻二氯苯；n-BuLi：正丁基锂；THF：四氢呋喃；m-xylene：间二甲苯；BBr3：三溴化硼；iPr2NEt：N,N-二异丙基乙胺；(t-Bu)3PHBF4：三叔丁基膦四氟硼酸盐；PA：特戊酸；CH3MgBr：甲基溴化镁；Cs2CO3：碳酸铯。
实施例1
本实施例的目标化合物1的合成路线如下：
合成步骤：
1.1中间体1-a的合成：在500mL双口烧瓶中加入1-溴-2，6-二氯苯(11.3g，50mmol)、2，4-二溴咔唑(19.5g，60mmol)、无水碳酸钾(9.66g，70mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(150mL)，然后在150℃下反应48h。待反应降至室温后，用二氯甲烷(300mL×3)萃取3次后，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体1-a(22.14g，产率85％)。
1.2中间体1-b的合成：在500mL双口烧瓶中加入中间体1-a(18g，42mmol)、9,9-二甲基-9,10-二氢吖啶(10.45g，50mmol)、三(二亚苄基丙酮)二钯(1.93g,2.1mmol)、2-二环己基膦-2’,6’-二甲氧基-1,1’-联苯(1.72g,4.2mmol)，叔丁醇钠(8.06g,84mmol)，在氩气氛围下抽通三次，加入超干甲苯(150mL),然后在110℃下反应48h。待反应降至室温后，用二氯甲烷(DCM)(300mL×3)萃取3次后，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体1-b(22.6g，产率80％)。
1.3中间体1-c的合成：向500mL反应瓶中加入中间体1-b(22.6g,33mmol)、间二甲苯330mL，在-78℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(13.2mL，17.2M，33.66mmol)并搅拌一h后在60℃下加热搅拌2h，然后减压蒸馏除去低沸点溶剂。在-78℃滴加三溴化硼(9.3g，37mmol)后，室温搅拌1h，再在0℃滴加N，N-二异丙基乙胺(4.9g，37mmol)后在140℃ 下加热搅拌24h。冷却至室温，加入醋酸钠水溶液并搅拌，DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体1-c(9.6g，15mmol，产率50％)。
1.4中间体1-d的合成：在500mL双口烧瓶中加入中间体1-c(9.6g，15mmol)，9，9-二甲基-9，10-二氢吖啶(6.27g，30mmol)，醋酸钯(180mg，0.75mmol)，三叔丁基膦四氟硼酸盐(705mg，2.25mmol)，叔丁醇钠(2.88g，30mmol)，在氩气氛围下抽通三次，加入无水甲苯(150mL),然后在110℃下反应36h。待反应降至室温后，用二氯甲烷(DCM)(200mL×3)萃取3次后，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体1-d(11.6g，产率80％)。
1.5目标化合物1的合成：在500mL双口烧瓶中加入中间体1-d(11.6g，12mmol)，醋酸钯(269mg，1.2mmol)，氧化银(5.57g，24mmol)，在氩气氛围下抽通三次，加入特戊酸(120mL)，在150℃下反应6h后，加入无水碳酸钾(552mg，4mmol)，继续反应12h，待反应降至室温后，加入饱和碳酸氢钠水溶液并搅拌，后用DCM萃取有机层，浓缩后经柱层析分离纯化得到，产物目标化合物1(5g，5.4mmol，产率45％)。
实施例2
本实施例的目标化合物2的合成路线如下：
合成步骤：
2.1中间体2-a的合成：在250mL的双口烧瓶中加入10,15-二氢-5H-二吲哚并[3,2-A:3',2'-C]咔唑(20.7g，60mmol)、2-溴碘苯(44.7g，150mmol)、碘化亚铜(0.57g，3mmol)、铜粉(7.5g，120mmol)和碳酸钾(16.5g，120mmol)，在氩气氛围下抽通3次，加入无水邻二氯苯(150mL)，在220℃下反应50h，反应结束后冷却至室温，用DCM和水萃取3次，合并有机相并去除溶剂，经柱层析得到中间体2-a(6g，9mmol，产率15％)。
2.2中间体2-b的合成：在500mL的双口烧瓶中加入中间体2-a(6g，9mmol)，在氩气氛围下抽通3次，加入无水四氢呋喃(200mL)，然后将装置放入到-78℃的干冰/丙酮浴中冷却15min，将(45mL，18mmol)的正丁基锂 的正己烷溶液用注射器逐滴加入到反应瓶中，在-78℃下再反应1h。再加入二苯基氯硅烷，在室温下反应12h，然后冷却至室温。用DCM和水萃取3次，合并有机相并去除溶剂，经柱层析得到中间体2-b(5.4g，产率60％)。
2.3中间体2-c的合成：在500mL的双口烧瓶中加入中间体2-b(4.3g，5mmol)、3，3-二甲基-1-丁烯(3.2mL，25mmol)、RhCl(PPh3)3(46mg，0.05mmol)，在氩气氛围下抽通3次，加入无水1,4-二氧六环(100mL)，在135℃下反应24h，反应结束后冷却至室温，用DCM和水萃取3次，合并有机相并去除溶剂，经柱层析得到中间体2-c(1.8g，产率84％)。
2.4中间体2-d的合成：在500mL双口烧瓶中加入1-溴-2，6-二氯苯(452mg，2mmol)，吩噻嗪(400mg，2mmol)，三(二亚苄基丙酮)二钯(184mg,0.2mmol)，2-二环己基膦-2′,6′-二甲氧基-1，1’-联苯(82mg，0.2mmol)，叔丁醇钠(240mg,2.5mmol)在氩气氛围下抽通三次，加入超干甲苯(200mL)，然后在110℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体2-d(577mg，产率75％)。
2.5中间体2-e的合成：在100mL双口瓶中加入中间体2-d(385mg，1mmol)，中间体2-c(860mg，1mmol)，无水碳酸钾(276mg，2mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(10mL),然后在150℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体2-e(800mg，产率76％)
2.6化合物2的合成：在100mL双口瓶中加入中间体2-e(600mg，0.5mmol)、间二甲苯10mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(1mol/L，0.2mL，0.51mmol)并搅拌1h。接着在-78℃滴加三溴化硼(190mg，0.75mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(100mg，0.75mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到产物化合物2(250mg，0.225mmol，产率45％)。
实施例3
本实施例的目标化合物3的合成路线如下：
合成步骤：
3.1中间体3-a的合成：在1000mL反应瓶中加入2,4-二溴咔唑(13.0g，40mmol)、吩噁嗪(6.41g，35mmol)、醋酸钯(420mg，1.75mmol)、三叔丁基膦四氟硼酸盐(1.0g，3.5mmol)、叔丁醇钠(2.45g，42mmol)，在氩气氛围下抽通三次，加入无水甲苯(400mL)，然后在110℃下回流反应36h。待反应降至室温后，用DCM萃取3次，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体3-a(10.2g，24mmol,产率70％)。
3.2中间体3-b的合成：在500mL双口瓶中加入中间体3-a(10.2g，24mmol)、吩噻嗪(4.88g，24mmol)、醋酸钯(288mg，1.2mmol)、三叔丁基膦四氟硼酸盐(680mg，2.4mmol)，叔丁醇钠(1.75g，30mmol)，在氩气氛围下抽通三次，加入无水甲苯(250mL)，然后在110℃下回流反应36h。待反应降至室温后，用DCM萃取3次，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体3-b(9.8g，18mmol，产率75％)。
3.3中间体3-c的合成：在500mL双口瓶中加入中间体3-b(9.8g，18mmol)、醋酸钯(410.4mg，1.8mmol)、氧化银(4.17g，18mmol)，在氩气氛围下抽通三次，加入特戊酸(180mL)，在150℃下反应6h后，加入无水 碳酸钾(412mg，3mmol)，继续反应12h，待反应降至室温后，加入饱和碳酸氢钠水溶液并搅拌至溶液体系pH为中性，后用DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体3-c(4.87g，9mmol，产率50％)。
3.4中间体3-d的合成：在250mL双口烧瓶中加入1-溴-2，6-二氯苯(2.71g，12mmol)、9，9-二甲基-9，10-二氢吖啶(2.51g，12mmol)、三(二亚苄基丙酮)二钯(265mg,0.6mmol)、2-二环己基膦-2’,6’-二甲氧基-1，1’-联苯(491mg,1.2mmol)、叔丁醇钠(1.92g,20mmol)在氩气氛围下抽通三次，加入超干甲苯(100mL),然后在110℃下反应48h。待反应降至室温后，用二氯甲烷(DCM)(200mL×3)萃取3次后，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体3-d(3.8g，9.6mmol,产率80％)。
3.5中间体3-e的合成：在250mL双口烧瓶中加入中间体3-d(3.8g，9mmol)，中间体3-c(4.87g，9mmol)，无水碳酸钾(2.07g，15mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(90mL),然后在150℃下反应48h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体3-e(6.3g，7mmol,产率80％)。
3.6目标化合物3的合成：向250mL反应瓶中加入中间体3-e(6.3g,7mmol)、对二甲苯140mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(2.8mL，3.65M，7.14mmol)并搅拌1h。接着在-78℃滴加三溴化硼(2.5g，10mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(1.27g，10mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到目标化合物3(2.33g，2.8mmol，产率40％)。
实施例4
本实施例的目标化合物4的合成路线如下：
合成步骤：
4.1中间体4-a的合成：在氩气氛围下，在100mL双口烧瓶中称取三聚吲哚(3.45g，10mmol)、碘化亚铜(380mg，2mmol)、铜粉(5g，80mmol)和碳酸钾(11g，80mmol)，加入50mL邻二氯苯、3.2mL邻碘苯甲酸甲酯(20mmol)，升温至220℃，在氩气保护下搅拌50h，然后冷却至室温，加入DCM和水萃取，分离有机相，加入无水硫酸钠干燥，将过滤所得有机相去除溶剂，经柱层析分离纯化得到中间体4-a(1.4g，产率：23％)
4.2中间体4-b的合成：在氩气氛围下，在100mL双口烧瓶中加入中间体4-a(1.2g，2mmol)，加18mL无水四氢呋喃，搅拌，然后滴加甲基溴化镁20mL(20mmol)，在80℃下反应12h后冷却至室温，加入乙酸乙酯和水萃取，分离有机相，加入无水硫酸钠干燥，将过滤所得有机相去除溶剂，经柱层析分离纯化得到中间体4-b(0.37g，0.6mmol，产率：30％)。
4.3中间体4-c的合成：在氩气氛围下，在100mL单口烧瓶中称取中间 体4-b(0.61g，1mmol)，加入20mL冰醋酸，再加入3mL浓盐酸，加热到130℃，反应4h，然后冷却至室温，加入二氯甲烷和水萃取，分离有机相，加入无水硫酸钠干燥，将过滤所得有机相去除溶剂，经柱层析分离纯化得到中间体4-c(0.35g，产率60％)
4.4中间体4-d的合成：在100mL双口烧瓶中加入1-溴-2,6-二氯苯(452mg，2mmol)、10H-吩硒嗪(492mg，2mmol)、三(二亚苄基丙酮)二钯(184mg,0.2mmol)、2-二环己基膦-2’,6’-二甲氧基-1,1’-联苯(82mg,0.2mmol)、叔丁醇钠(240mg，2.5mmol)在氩气氛围下抽通三次，加入超干甲苯(20mL),然后在110℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体4-d(652mg，1.5mmol,产率75％)。
4.5中间体4-e的合成：在100mL双口瓶中加入中间体4-d(440mg，1mmol)、中间体4-c(575mg，1mmol)、无水碳酸钾(280mg，2mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(20mL)，然后在150℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体(750mg，0.75mmol，产率75％)
4.6目标化合物4的合成：在100mL双口中加入中间体4-e(500mg，0.5mmol)，间二甲苯10mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(0.2mL，1M，0.51mmol)并搅拌1h。接着在-78℃滴加三溴化硼(188mg，0.75mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(100mg，0.75mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到目标化合物4(202mg，0.2mmol，产率40％)。
实施例5
本实施例的目标化合物5的合成路线如下：
合成步骤：
5.1中间体5-a的合成：在氩气氛围下，在100mL双口烧瓶中称取三聚吲哚(3.45g，10mmol)、1-(2-溴苯氧基)-2-丁酮(13g，50mmol)、碘化亚铜(0.19g，1mmol)、铜粉(2.5g，40mmol)和碳酸钾(5.5g，40mmol)，加入50mL邻二氯苯，升温至220℃反应50h，然后冷却至室温，加入二氯甲烷和水萃取，分离有机相，加入无水硫酸钠干燥，通过旋转蒸发仪去除溶剂，经柱层析分离得到中间体5-a(1.5g，2mmol，产率：20％)。
5.2中间体5-b的合成：将中间体5-a(1.5g，2mmol)和CF3SO3H加入到100mL双口烧瓶中，将混合物在室温下搅拌24h，然后加入水和吡啶的混合物(体积比8:1)，搅拌30分钟，将搅拌的混合物冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体5-b(0.23g，产率：35％)
5.3中间体5-c的合成：在250mL双口烧瓶中加入1-溴-2,6-二氯苯(2.26g，10mmol)、氘代3,6-二叔丁基咔唑(2.85g，10mmol)、碳酸钾(2.76g，20mmol),在氩气氛围下抽通三次，加入超干二甲亚砜(20mL)，然后在150℃ 下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体5-c(3.5g，7.5mmol，产率75％)。
5.4中间体5-d的合成：在250mL双口烧瓶中加入中间体5-c(470mg，1mmol)、中间体5-b(525mg，1mmol)、无水碳酸钾(414mg，3mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(20mL),然后在150℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体5-d(673mg，产率70％)
5.5目标化合物5的合成：在100mL双口瓶中加入中间体5-d(480mg，0.5mmol)、，间二甲苯10mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(0.2mL，1M，0.51mmol)并搅拌1h。接着在-78℃滴加三溴化硼(188mg，0.75mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(100mg，0.75mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到目标化合物5(204mg，0.23mmol，产率46％)。
实施例6
本实施例的目标化合物6的合成路线如下：
合成步骤：
6.1中间体6-a的合成：在1000mL反应瓶中加入2,3-二溴咔唑(19.5g，60mmol)、3,6-二叔丁基咔唑(16.74g，60mmol)、碳酸铯(21.2g，65mmol)，在氩气氛围下抽通三次，加入N，N-二甲基甲酰胺(700mL)，在110℃下反应36h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体6-a(23.5g，45mmol,产率75％)。
6.2中间体6-b的合成：在1000mL反应瓶中加入中间体6-a(23.5g,45mmol)，吩噁嗪(9.15g，50mmol)、醋酸钯(600mg，2.5mmol)、三叔丁基膦四氟硼酸盐(1.41g，5mmol)、叔丁醇钠(5.76g，60mmol)，在氩气氛围下抽通三次，加入无水甲苯(200mL)，然后在110℃下反应36h。待反应降至室温后，用DCM萃取3次，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体6-b(22g，产率80％)。
6.3中间体6-c的合成：在500mL双口瓶中加入中间体6-b(22g，36mmol) 醋酸钯(807mg，3.6mmol)、氧化银(16.71g，72mmol)，在氩气氛围下抽通三次、加入特戊酸(360mL)，在150℃下反应6h后，加入无水碳酸钾(1.65g，12mmol)，继续反应12h，待反应降至室温后，加入饱和碳酸氢钠水溶液并搅拌，后用DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体6-c(11.2g，18mmol，产率50％)。
6.4中间体6-d的合成：在500mL双口烧瓶中加入1-溴-2，6-二氯苯(6.78g，30mmol)、吩噻嗪(5.97g，30mmol)、三(二亚苄基丙酮)二钯(2.76g，3mmol)、2-二环己基膦-2′,6′-二甲氧基-1,1’-联苯(1.23g,3mmol)、叔丁醇钠(3.6g,37.5mmol)在氩气氛围下抽通三次，加入超干甲苯(300mL),然后在110℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体6-d(8.4g，产率75％)。
6.5中间体6-e的合成：在500mL双口烧瓶中加入中间体6-d(8.4g，18mmol)、中间体6-c(11.2g，18mmol)、无水碳酸钾(2.76g，20mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(150mL),然后在150℃下反应48h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体6-e(22.14g，产率80％)。
6.6目标化合物6的合成：向500mL反应瓶中加入中间体6-e(22.1g,14mmol)、对二甲苯280mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(5.6mL，7.3mol/L，14.28mmol)并搅拌1h。接着在-78℃滴加三溴化硼(5g，20mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(2.58g，20mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到目标化合物6(6.4g，7.1mmol，产率45％)。
实施例7
本实施例的目标化合物7的合成路线如下：
合成步骤：
7.1中间体7-a的合成：在1000mL反应瓶中加入2,3-二溴咔唑(9.75g，30mmol)、9,9-二苯基-9，10-二氢吖啶(23.34g,70mmol)、醋酸钯(720mg，3mmol)、三叔丁基膦四氟硼酸盐(1.69g，6mmol)、叔丁醇钠(6.72g，70mmol)，在氩气氛围下抽通三次，加入无水甲苯(400mL)，然后在110℃下反应48h。待反应降至室温后，用DCM萃取3次，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体7-a(17.4g，21mmol,产率70％)。
7.2中间体7-b的合成：在500mL双口瓶中加入中间体7-a(17.4g，21mmol)、醋酸钯(471mg，2.1mmol)、氧化银(9.75g，42mmol)，在氩气氛围下抽通三次，加入特戊酸(210mL)，在150℃下反应6h后，加入无水碳酸钾(973mg，7mmol)，继续反应12h，待反应降至室温后，加入饱和碳酸氢钠水溶液并搅拌，后用DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体7-b(8.25g，10mmol，产率48％)。
7.3中间体7-c的合成：在500mL双口烧瓶中加入1-溴-2,6-二氯苯(4.52g，20mmol)、9,9-二苯基-9,10-二氢吖啶(5.97g，19mmol)、三(二亚苄基丙酮)二钯(920mg，1mmol)、2-二环己基膦-2′,6′-二甲氧基-1,1’-联苯(410mg，1mmol)、叔丁醇钠(2.4g,25mmol)在氩气氛围下抽通三次，加入超干甲苯(300mL)，然后在110℃下回流反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体7-c(8.33g，16mmol，产率80％)。
7.4中间体7-d的合成：在500mL双口烧瓶中加入中间体7-c(5.21g，10mmol)、中间体7-b(8.25g，10mmol)、无水碳酸钾(2.1g，15mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(100mL),然后在150℃下反应36h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体7-d(9.17g，7mmol，产率70％)。
7.5目标化合物7的合成：向500mL双口瓶中加入中间体7-d(9.17g，7mmol)、对二甲苯140mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(2.8mL，3.6M，7.14mmol)并搅拌1h。接着在-78℃滴加三溴化硼(2.5g，10mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(1.27g，10mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到产物目标化合物7(3.7g，3mmol，产率43％)。
实施例8
本实施例的目标化合物8的合成路线如下：
合成步骤：
8.1中间体8-a的合成：在1000mL双口烧瓶中加入4-溴-3,5-二氯苄腈(12.5g，50mmol)、2，4-二溴咔唑(19.5g，60mmol)、无水碳酸钾(9.66g，70mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(150mL)，然后在150℃下反应48h。待反应降至室温后，用二氯甲烷(DCM)(300mL×3)萃取3次后，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体8-a(20.36g，产率76％)。
8.2中间体8-b的合成：在1000mL双口烧瓶中加入中间体1-a(16.1g，30mmol)、9H-吡啶[3,4-b]吲哚(5.55g，33mmol)、三(二亚苄基丙酮)二钯(1.37g,1.5mmol)、2-二环己基膦-2’,6’-二甲氧基-1,1’-联苯(1.23g,3mmol)、叔丁醇钠(3.84g,40mmol)在氩气氛围下抽通三次，加入超干甲苯(300mL),然后在110℃下反应48h。待反应降至室温后，用二氯甲烷(DCM)(300mL×3)萃取3次后，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体8-b(14g，产率70％)。
8.3中间体8-c的合成：向500mL反应瓶中加入中间体8-b(13.4g,20 mmol)、间二甲苯200mL，在-78℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(8.2mL，2.5M，20.4mmol)并搅拌1h后，在60℃下加热搅拌2h，然后减压蒸馏除去低沸点溶剂。在-78℃滴加三溴化硼(5.64g，22.4mmol)后，室温搅拌1h，再在0℃滴加N，N-二异丙基乙胺(2.96g，22.4mmol)后，在140℃下加热搅拌24h。冷却至室温，加入醋酸钠水溶液并搅拌，DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体8-c(4.9g，8.2mmol，产率40％)。
8.4中间体8-d的合成：在500mL双口烧瓶中加入中间体8-c(3g，5mmol)，2,3-苯并咔唑(1.3g，6mmol)、醋酸钯(56mg，0.25mmol)、三叔丁基膦四氟硼酸盐(145mg，0.5mmol)、叔丁醇钠(960mg，10mmol)，在氩气氛围下抽通三次，加入无水甲苯(50mL)，然后在110℃下反应36h。待反应降至室温后，用二氯甲烷(100mL×3)萃取3次后，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体8-d(3g，产率70％)。
8.5目标化合物8的合成：在200mL双口瓶中加入中间体8-d(4.36g，5mmol)、醋酸钯(112mg，0.5mmol)、氧化银(2.31g，10mmol)，在氩气氛围下抽通三次，加入特戊酸(50mL)，在150℃下反应6h后，加入无水碳酸钾(135mg，1mmol)，继续反应12h，待反应降至室温后，加入饱和碳酸氢钠水溶液并搅拌，后用DCM萃取有机层，浓缩后经柱层析分离纯化得到目标化合物8(1.8g，2.1mmol，产率42％)。
实施例9
本实施例的目标化合物9的合成路线如下：
合成步骤：
9.1中间体9-a的合成：在1000mL反应瓶中加入2,3-二溴咔唑(19.5g，60mmol)、3,6-二叔丁基咔唑(16.74g，60mmol)、碳酸铯(21.2g，65mmol)，在氩气氛围下抽通三次，加入N，N-二甲基甲酰胺(700mL)，在110℃下反应36h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体9-a(23.5g，产率75％)。
9.2中间体9-b的合成：在1000mL反应瓶中加入中间体9-a(23.5g，45mmol)、5-苯基-5,11-二氢吲哚并[3,2-B]咔唑(16.6g，50mmol)、醋酸钯(600mg，2.5mmol)，三叔丁基膦四氟硼酸盐(1.41g，5mmol)、叔丁醇钠(5.76g， 60mmol)，在氩气氛围下抽通三次，加入无水甲苯(400mL),然后在110℃下反应36h。待反应降至室温后，用DCM萃取3次，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体9-b(23.7g，产率68％)。
9.3中间体9-c的合成：在500mL双口瓶中加入中间体9-b(23.2g，30mmol)、醋酸钯(672mg，3mmol)、氧化银(13.9g，60mmol)，在氩气氛围下抽通三次，加入特戊酸(360mL)，在150℃下反应6h后，加入无水碳酸钾(1.38g，10mmol)，继续反应12h，待反应降至室温后，加入饱和碳酸氢钠水溶液并搅拌，后用DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体9-c(9.9g，12.9mmol，产率43％)。
9.4中间体9-d的合成：在500mL双口烧瓶中加入4-溴-3,5-二氯三氟甲苯(5.88g，20mmol)、苯并[b][1,8]萘吡啶(4.63g，22mmol)、三(二亚苄基丙酮)二钯(1.83g，2mmol)、2-二环己基膦-2’,6’-二甲氧基-1,1’-联苯(821mg，2mmol)、叔丁醇钠(2.4g,25mmol)在氩气氛围下抽通三次，加入超干甲苯(200mL)，然后在110℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体9-d(6.05g，产率65％)。
9.4中间体9-e的合成：在500mL双口烧瓶中加入中间体9-d(5.59g，12mmol)、中间体9-c(9.2g，18mmol)、无水碳酸钾(2.8g，20mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(150mL),然后在150℃下反应48h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体9-e(10.8g，9mmol，产率75％)。
9.4目标化合物9的合成：向500mL反应瓶中加入中间体9-e(10.8g，9mol)、对二甲苯90mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(3.7mL，9.18mmol)并搅拌1h。接着在-78℃滴加三溴化硼(2.7g，10.8mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(1.39g，10.8mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到产物目标化合物9(3.9g，3.5mmol，产率38％)。
实施例10
本实施例的目标化合物10的合成路线如下：
合成步骤：
10.1中间体10-a的合成：在1000mL反应瓶中加入2,3-二溴咔唑(9.75g，30mmol)、9,9-二苯基-9,10-二氢吖啶(11.67g，35mmol)、醋酸钯(360mg，1.5mmol)、三叔丁基膦四氟硼酸盐(845mg，3mmol)、叔丁醇钠(3.84g，40mmol)，在氩气氛围下抽通三次，加入无水甲苯(400mL)，然后在110℃下反应48h。待反应降至室温后，用DCM萃取3次，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体10-a(11.9g，20.5mmol,产率68％)。
10.2中间体10-b的合成：在500mL反应瓶中加入中间体10-a(11.5g，20mmol)、6,6-二甲基-6,11-二氢-13-氧杂-11-氮杂吲哚[1,2-b]蒽(6.59g，22mmol)、醋酸钯(225mg，1mmol)、三叔丁基膦四氟硼酸盐(564mg，2mmol)、叔丁醇钠(2.30g，24mmol)，在氩气氛围下抽通三次，加入无水甲苯(200mL),然后在110℃下反应36h。待反应降至室温后，用DCM萃取3次，用旋转蒸发仪去除多余溶剂后，再经柱层析分离纯化得到中间体10-b(10.3g，13mmol， 产率65％)。
10.3中间体10-c的合成：在500mL双口瓶中加入中间体10-b(8g，10mmol)、醋酸钯(225mg，1mmol)、氧化银(4.64g，20mmol)，在氩气氛围下抽通三次，加入特戊酸(100mL)，在150℃下反应6h后，加入无水碳酸钾(690mg，5mmol)，继续反应12h，待反应降至室温后，加入饱和碳酸氢钠水溶液并搅拌，后用DCM萃取有机层，浓缩后经柱层析分离纯化得到中间体10-c(3.72g，4.7mmol，产率47％)。
10.4中间体10-d的合成：在500mL双口烧瓶中加入4-溴-3,5-二氯三氟甲苯(2.94g，10mmol)、4-甲基-10氢吩噁嗪(1.35g，12mmol)、三(二亚苄基丙酮)二钯(915mg，1mmol)、2-二环己基膦-2’,6’-二甲氧基-1,1’-联苯(410mg，1mmol)、叔丁醇钠(1.34g，14mmol)在氩气氛围下抽通三次，加入超干甲苯(100mL),然后在110℃下反应24h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体10-d(2.69g，7mmol，产率70％)。
10.5中间体10-e的合成：在500mL双口烧瓶中加入中间体10-d(1.92g，5mmol)，中间体10-c(4g，5mmol)，无水碳酸钾(828mg，6mmol)，在氩气氛围下抽通三次，加入超干二甲亚砜(50mL),然后在150℃下反应48h。待反应降至室温后，用DCM萃取3次后，用旋转蒸发仪去除多余溶剂，再经柱层析分离纯化得到中间体10-e(4.16g，3.65mmol，产率73％)。
10.6目标化合物10的合成：向500mL反应瓶中加入中间体10-e(10.8g，3mol)、对二甲苯30mL，在-40℃下向反应体系中逐滴加入正丁基锂的正己烷溶液(1.22mL，3.06mmol)并搅拌1h。接着在-78℃滴加三溴化硼(0.9g，3.6mmol)后，室温搅拌1h，再在0℃下滴加N，N-二异丙基乙胺(465mg，3.6mmol)后在150℃下加热搅拌24h。冷却至室温，用DCM萃取有机层，浓缩后经柱层析分离纯化得到产物目标化合物10(1.08g，1mmol，产率35％)。
实施例1-10所合成的目标化合物及化合物A(结构式参考后文)的质谱(Mass Spectrometry，MS)和元素分析(EA)结果如下表1所示。
表1
下面通过具体器件实施例1-20及对比例1-2对包括上述化合物的电致发光器件的性能进行测试。其中，电致发光器件的膜层叠构示意图如图1所示，其中，1—玻璃和导电玻璃(ITO阳极)衬底层；2—空穴注入层(HATCN，10nm)；3—空穴传输层(TAPC，30nm)；4—电子阻挡层(TCTA，15nm)；5—发光层(20nm)；6—空穴阻挡层(DBFPO，20nm)；7—电子传输层(ANT-BIZ，30nm)；8—电子注入层(LiQ，1nm)；9—阴极(Al，100nm)。
其中，器件实施例1-20以及器件对比例1除了发光层的材料不同以外，其他器件结构及制作方法均相同。
器件对比例1的发光层：化合物A与主体发光材料mCBP，蒸镀比例为4:196。
器件对比例2的发光层：化合物A、光敏化剂Ir(ppy)3以及主体发光材料mCBP，蒸镀比例为2:20:178。
器件实施例1的发光层：与器件对比例1的区别在于，将化合物A替换为实施例1合成的化合物1。
器件实施例2的发光层：与器件对比例1的区别在于，将化合物A替换为实施例2合成的化合物2。
器件实施例3的发光层：与器件对比例1的区别在于，将化合物A替换为实施例3合成的化合物3。
器件实施例4的发光层：与器件对比例1的区别在于，将化合物A替换为实施例4合成的化合物4。
器件实施例5的发光层：与器件对比例1的区别在于，将化合物A替换为实施例5合成的化合物5。
器件实施例6的发光层：与器件对比例1的区别在于，将化合物A替换为实施例6合成的化合物6。
器件实施例7的发光层：与器件对比例1的区别在于，将化合物A替换 为实施例7合成的化合物7。
器件实施例8的发光层：与器件对比例1的区别在于，将化合物A替换为实施例8合成的化合物8。
器件实施例9的发光层：与器件对比例1的区别在于，将化合物A替换为实施例9合成的化合物9。
器件实施例10的发光层：与器件对比例1的区别在于，将化合物A替换为实施例10合成的化合物10。
器件实施例11的发光层：与器件对比例2的区别在于，将化合物A替换为实施例1合成的化合物1。
器件实施例12的发光层：与器件对比例2的区别在于，将化合物A替换为实施例2合成的化合物2。
器件实施例13的发光层：与器件对比例2的区别在于，将化合物A替换为实施例3合成的化合物3。
器件实施例14的发光层：与器件对比例2的区别在于，将化合物A替换为实施例4合成的化合物4。
器件实施例15的发光层：与器件对比例2的区别在于，将化合物A替换为实施例5合成的化合物5。
器件实施例16的发光层：与器件对比例2的区别在于，将化合物A替换为实施例6合成的化合物6。
器件实施例17的发光层：与器件对比例2的区别在于，将化合物A替换为实施例7合成的化合物7。
器件实施例18的发光层：与器件对比例2的区别在于，将化合物A替换为实施例8合成的化合物8。
器件实施例19的发光层：与器件对比例1的区别在于，将化合物A替换为实施例9合成的化合物9。
器件实施例20的发光层：与器件对比例2的区别在于，将化合物A替换为实施例10合成的化合物10。
上述电致发光器件可按本领域的已知方法制作，例如可按照参考文献(Adv.Mater.2003,15,277.)公开的方法制作。具体方法为：在高真空条件下， 在经过清洗的导电玻璃(ITO)衬底上依次蒸镀上述空穴注入层、空穴传输层、电子阻挡层、发光层，空穴阻挡层、电子传输层、电子注入层和阴极。用该方法制得如图1所示的器件。在电流密度10mA/cm2条件下记录所制备器件的发光特性，如下表2所示。其中，Voltage为器件的工作电压，CE为电流效率(current efficiency)，电流效率越高，器件的载流子使用率越高，发光效率越高。
表2

从表2可看出，相较于器件对比例1所制备的电致发光器件，本申请的实施例提供的器件实施例1-10所制备的电致发光器件具有更低的工作电压，更高的发光效率，以及更高的使用寿命。可能的原因是，本申请实施例提供的化合物，通过引入位阻较大的杂环芳烃片段，使得分子呈现一定程度的扭曲结构，能够有效抑制浓度淬灭效应，且通过引入氧硫等杂原子，有利于增强分子的自旋轨道耦合效应，从而使得分子具有短的延迟寿命，进而整体上提升器件的发光效率和使用寿命。
相比于器件实施例1-10所制备的电致发光器件，器件实施例11-20所制备的电致发光器件能够进一步降低工作电压，提高发光下来以及提升使用寿命，可能的原因是，通过在发光层中引入磷光材料，与本申请实施例提供的化合物搭配起来，高效的磷光材料可以捕获电致发光器件中的三线态激子，通过能量传递的方式将能量传递给荧光分子(本申请提供的化合物)使得荧光分子发光，在保持荧光分子窄光谱的同时，实现高效的三线态激子的利用，进而实现高效、高色纯度、高稳定性的电致发光器件。
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详述的部分，可以参见其他实施例的相关描述。
以上对本申请的实施例所提供的含硼类化合物、电致发光器件及显示面板进行了详细说明，以上说明只是用于帮助理解本申请的技术方案及其核心思想； 本领域的普通技术人员对前述各实施例所记载的技术方案进行修改或者对其中部分技术特征进行等同替换，并不使相应技术方案的本质脱离本申请各实施例的技术方案的范围。

Claims (20)

  1. 一种含硼类化合物，其中，所述含硼类化合物的结构通式如式(I)所示：
    各自独立地选自取代或未取代的C6-C60的芳基、或取代或未取代的C5-C60的杂芳基；
    R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
    R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5自独立地选自H、C1-C30的烷基、或C6-C30的芳基；
    G选自氮原子或膦氧基；
    X、Y、Z各自独立地选自碳原子或氮原子。
  2. 根据权利要求1所述的含硼类化合物，其中，选自以下结构中的任意一种：
    其中，“*”表示连接位点；
    R1每次出现时，独立地选自H、取代或未取代的C6-C40的芳基、或取代 或未取代的C5-C40的杂芳基；和/或，相邻的R1之间成环或不成环。
  3. 根据权利要求1所述的含硼类化合物，其中，所述含硼类化合物的结构通式如式(I-1)或式(I-2)所示：
    至各自独立地选自取代或未取代的C6-C30的芳基、或取代或未取代的C6-C30的杂芳基；
    R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
    R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5各自独立地选自H、C1-C30的烷基或C6-C30的芳基。
  4. 根据权利要求3所述的含硼类化合物，其中，所述含硼类化合物的结构通式如式(I-1-1)或式(I-2-1)所示：
    至各自独立地选自取代或未取代的C6-C30的芳基、或取代或未取代的C5-C30的杂芳基；
    R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
    R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5各自独立地选自H、C1-C30的烷基或C6-C30的芳基。
  5. 根据权利要求4所述的含硼类化合物，其中，至各自独立地选自取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的苯并噻吩基、取代或未取代的苯并呋喃基、取代或未取代的联苯基、取代或未取代的二苯并呋喃基、取代或未取代的咔唑基、取代或未取代的吲哚基、取代或未取代的萘基，或取代或未取代的喹唑啉基。
  6. 根据权利要求5所示的含硼类化合物，其中，至各自独立地选自被氘原子、-CH3、-C(CH3)3、-CF3、-CN或-OCH3取代或未取代的苯基、苯并噻吩基团、联苯基团、萘基、喹唑啉基团、被苯基取代的咔唑基团、或二苯并呋喃基团。
  7. 根据权利要求4所述的含硼类化合物，其中，R1、R2、R3各自独立地选自氢原子、-CN、-CF3或-OCH3。
  8. 根据权利要求4所述的含硼类化合物，其中，R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-，R4和R5各自独立地选自H、C1-C10的烷基或C6-C20的芳基。
  9. 根据权利要求4所述的含硼类化合物，其中，所述含硼类化合物选自如下结构式所示的化合物中的一种：


  10. 一种电致发光器件，其中，包括阳极和阴极，以及位于所述阳极和所 述阴极之间的发光层，所述发光层包括含硼类化合物，其中，所述化合物的结构通式如式(I)所示：
    各自独立地选自取代或未取代的C6-C60的芳基、或取代或未取代的C5-C60的杂芳基；
    R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
    R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5自独立地选自H、C1-C30的烷基、或C6-C30的芳基；
    G选自氮原子或膦氧基；
    X、Y、Z各自独立地选自碳原子或氮原子。
  11. 根据权利要求10所述的电致发光器件，其中，选自以下结构中的任意一种：
    其中，“*”表示连接位点；
    R1每次出现时，独立地选自H、取代或未取代的C6-C40的芳基、或取代或未取代的C5-C40的杂芳基；和/或，相邻的R1之间成环或不成环。
  12. 根据权利要求10所述的电致发光器件，其中，所述含硼类化合物的结构通式如式(I-1)或式(I-2)所示：
    至各自独立地选自取代或未取代的C6-C30的芳基、或取代或未取代的C6-C30的杂芳基；
    R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
    R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5各自独立地选自H、C1-C30的烷基或C6-C30的芳基。
  13. 根据权利要求12所述的电致发光器件，其中，所述含硼类化合物的结构通式如式(I-1-1)或式(I-2-1)所示：
    至各自独立地选自取代或未取代的C6-C30的芳基、或取代或未取代的C5-C30的杂芳基；
    R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
    R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5各自独立地选自H、C1-C30的烷基或C6-C30的芳基。
  14. 根据权利要求13所述的电致发光器件，其中，至各自独立地选自取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的苯并噻吩基、取代或未取代的苯并呋喃基、取代或未取代的联苯基、取代或未取代的二苯并呋喃基、取代或未取代的咔唑基、取代或未取代的吲哚基、取代或未取代的萘基，或取代或未取代的喹唑啉基。
  15. 根据权利要求14所示的电致发光器件，其中，至各自独立地选自被氘原子、-CH3、-C(CH3)3、-CF3、-CN或-OCH3取代或未取代的苯基、苯并噻吩基团、联苯基团、萘基、喹唑啉基团、被苯基取代的咔唑基团、或二苯并呋喃基团。
  16. 根据权利要求13所述的电致发光器件，其中，R1、R2、R3各自独立地选自氢原子、-CN、-CF3或-OCH3。
  17. 根据权利要求13所述的电致发光器件，其中，R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-， R4和R5各自独立地选自H、C1-C10的烷基或C6-C20的芳基。
  18. 根据权利要求13所述的电致发光器件，其中，所述含硼类化合物选自如下结构式所示的化合物中的一种：


  19. 一种显示面板，其中，所述显示面板包括电致发光器件，所述电致发 光器件包括含硼类化合物，其中，所述含硼类化合物的结构通式如式(I)所示：
    各自独立地选自取代或未取代的C6-C60的芳基、或取代或未取代的C5-C60的杂芳基；
    R1、R2、R3各自独立地选自氢原子、氘原子、卤素原子、-CN、-NO2、-CF3、-OH、-SH、-NH2、C1-C30的直链烃基、C3-C30的支链烃基、C3-C30的环烷基、C1-C30的烷氧基、C1-C30的烷硫基、C6-C60的芳基、C6-C60的芳醚基、C5-C60的杂芳基或C5-C60的杂芳醚基；
    R每次出现时，独立地选自单键、-CR4R5-、-CO-、-SiR4R5-、-NR4-、-POR4-、-O-、-S-、-Se-、-Te-、-SO-或-SO2-；R4和R5自独立地选自H、C1-C30的烷基、或C6-C30的芳基；
    G选自氮原子或膦氧基；
    X、Y、Z各自独立地选自碳原子或氮原子。
  20. 根据权利要求19所述的显示面板，其中，所述显示面板还包括像素驱动电路，所述像素驱动电路与所述电致发光器件电连接。
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CN116253753A (zh) * 2022-12-22 2023-06-13 清华大学 一种发光材料及其应用以及包含其的有机电致发光器件
CN118388514A (zh) * 2024-04-19 2024-07-26 武汉华星光电半导体显示技术有限公司 含硼类化合物、电致发光器件及显示面板

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