WO2022042479A1 - Compound and application thereof - Google Patents

Compound and application thereof Download PDF

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Publication number
WO2022042479A1
WO2022042479A1 PCT/CN2021/114065 CN2021114065W WO2022042479A1 WO 2022042479 A1 WO2022042479 A1 WO 2022042479A1 CN 2021114065 W CN2021114065 W CN 2021114065W WO 2022042479 A1 WO2022042479 A1 WO 2022042479A1
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ring
formula
substituted
group
unsubstituted
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PCT/CN2021/114065
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French (fr)
Chinese (zh)
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李国孟
曾礼昌
李熠烺
孙磊
徐超
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北京鼎材科技有限公司
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Publication of WO2022042479A1 publication Critical patent/WO2022042479A1/en

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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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    • 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
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • 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
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
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    • C09K2211/1011—Condensed systems
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    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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    • 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

Definitions

  • the present invention relates to the technical field of organic electroluminescence, in particular to a compound and its application.
  • OLEDs Organic electroluminescent diodes
  • red and green dyes which are three primary colors, generally contain heavy atoms such as Ir, Pt, etc., can theoretically achieve 100% internal quantum efficiency, high electroluminescence efficiency, and low power consumption.
  • Mainstream display devices the chromaticity and lifetime of blue phosphorescent materials cannot meet the current commercial display requirements. At present, blue light devices still use traditional fluorescent materials to achieve high color purity and long device lifetime.
  • CN110662750A discloses a class of boron-containing organic materials.
  • cyclohexane is preferably used as a steric hindrance group, and the main purpose is to reduce the concentration quenching in the device.
  • the performance of organic electroluminescent devices using this organic material still needs to be improved.
  • One of the objectives of the present invention is to provide a compound, especially a boron-containing compound, which is a blue fluorescent material.
  • the compound When the compound is applied to an organic electroluminescence device, the device performance can be improved and the driving voltage can be reduced. Improve device efficiency.
  • the present invention provides a compound represented by a parent nucleus represented by formula (1) and at least one (eg 1, 2, 3, 4, 5 or 6, etc.) represented by formula (H) and the substituent shown in formula (H) is substituted at any substitutable position of the parent nucleus shown in formula (1);
  • * represents the connecting bond of the group
  • the ring D, ring G and ring F are independently selected from a substituted or unsubstituted C5-C60 aromatic ring or a substituted or unsubstituted C3-C60 heteroaromatic ring, the substituted or unsubstituted C3-C60 heteroaromatic ring.
  • the group is connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring;
  • the "connected to form a ring or not to form a ring” refers to when a C6-C60 aromatic ring or a C3-C60 heteroaromatic ring
  • the substituent can be connected with the substituted aromatic ring or heteroaromatic ring to form a ring structure, or it can be substituted on the aromatic ring or heteroaromatic ring only by single bond substitution, wherein the way of connecting into a ring
  • it can be exemplarily connected by a single bond, or it can be connected by a connecting group such as a methylene group.
  • the X 1 and X 2 are independently selected from one of CR 1 R 2 , NR 3 , O, S or SiR 4 R 5 , the R 1 , R 2 , R 3 , R 5 4 and R 5 are independently connected to the adjacent ring D, ring G or ring F to form a ring or not to form a ring; when there are two R 3 in the compound at the same time, the two R 3 can be selected from the same group , can also be selected from different groups, R 1 , R 2 , R 4 and R 5 are the same;
  • R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 cycloalkyl
  • One of C6-C60 aryl group, substituted or unsubstituted C3-C60 heteroaryl group, the substituted group is connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring;
  • the ring A and ring E are independently selected from substituted or unsubstituted C3-C8 aliphatic rings, and the substituted group is connected to the connected aliphatic ring to form a ring or not to form a ring;
  • C3-C8 means that the aliphatic ring contains 3-8 carbon atoms, and the number includes the carbon atoms shared by ring A and ring E;
  • the ring A and the ring E are connected by sharing a sp3 hybridized C atom; sharing a sp3 hybridized C atom for connection, that is, a spiro ring structure is formed;
  • the substituted groups are independently selected from halogen, cyano, carbonyl, nitro , hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6- One or a combination of at least two C60 aryl groups and C3-C60 heteroaryl groups.
  • the aromatic ring in the present invention refers to the cyclic structure of an aryl group, and for a specific example, reference can be made to the aryl moiety in this specification.
  • the heteroaromatic ring in the present invention refers to a cyclic structure of a heteroaryl group, and for specific examples, reference can be made to the heteroaryl group in this specification.
  • substituted group refers to the selection range of the substituent when the “substituted or unsubstituted” group is substituted, and the number is not specifically limited, as long as it meets the requirements of compound bonds. There may be 1, 2, 3, 4 or 5, and when the number of substituents is 2 or more, the 2 or more substituents may be the same or different.
  • halogen represents a chlorine atom, a fluorine atom, a bromine atom or the like.
  • the expressions of Ca-Cb represent that the number of carbon atoms of the group is a-b, unless otherwise specified, generally the number of carbon atoms does not include the number of carbon atoms of the substituent.
  • the expression of the ring structure crossed by "—" means that the connection site is at any position on the ring structure that can form a bond.
  • the aryl group includes a monocyclic aryl group or a fused-ring aryl group
  • the heteroaryl group includes a monocyclic heteroaryl group or a fused-ring heteroaryl group.
  • C6 (or C5) to C60 (such as C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44 , C46, C48, C50, C52, C54, C56, C58, etc.)
  • aryl (or aromatic ring) is preferably a substituted or unsubstituted C6-C30 aryl (aromatic ring), more preferably a substituted or unsubstituted C6- C20 aryl group (aromatic ring), more preferably a group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl and derivatives thereof, fluoranthene, triphenylene, Pyrene, perylene, A group in the group consisting of radical and nap
  • biphenyl is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl groups include 1-naphthyl and 2-naphthyl; anthracenyl is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene;
  • the C6-C60 arylamino group represents a group formed by connecting a C6-C60 aryl group and an amino group through a single bond, wherein the C6-C60 aryl group is as described in the previous paragraph.
  • the heteroatoms mentioned in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, preferably selected from N, O, S.
  • the atom names described in the present invention include their corresponding isotopes, for example, hydrogen (H) includes 1 H (protium or H), 2 H (deuterium or D), etc.; carbon (C) includes 12C , 13C , etc.
  • C3 to C60 (such as C4, C5, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42 , C44, C46, C48, C50, C52, C54, C56, C58, etc.) heteroaryl (heteroaryl ring) is preferably C3 ⁇ C30 heteroaryl (heteroaryl ring), more preferably C4 ⁇ C20 heteroaryl ( heteroaromatic ring), more preferably nitrogen-containing heteroaryl, oxygen-containing heteroaryl, sulfur-containing heteroaryl, etc.
  • carbazolyl and derivatives thereof wherein the carbazolyl derivative is preferably 9-phenylcarbazole , 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolocarbazole.
  • the C3-C60 heteroaryl group represents a group formed by connecting a C3-C60 heteroaryl group and an amino group through a single bond, wherein the C3-C60 heteroaryl group is the same as that described in the previous paragraph.
  • the above-mentioned C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, more preferably a C1-C6 chain alkyl group, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, tert-butyl, etc.
  • C3-C20 cycloalkyl includes monocycloalkyl and polycycloalkyl, wherein polycycloalkyl refers to an alkyl group containing at least two ring structures.
  • the C3-C20 cycloalkyl group is preferably a C3-C12 cycloalkyl group, more preferably a C3-C10 cycloalkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cycloheptyl etc.
  • the C1-C20 alkoxy group is preferably a C1-C10 alkoxy group, more preferably a C1-C6 alkoxy group, and examples thereof include a methoxy group and an ethoxy group.
  • the C1-C20 silyl group is preferably a C1-C10 silyl group, more preferably a C1-C6 silyl group, and examples thereof include methylsilane, ethylsilane, isopropylsilane, tert-butylsilane, and phenylsilane. Wait.
  • the present invention provides a new type of boron-containing compound.
  • a group containing a spiroalkane structure is introduced into the boron-containing parent core, and the spiroalkane structure can effectively play a steric hindrance role and improve efficiency;
  • the structure can effectively improve the molecular transition dipole arrangement and achieve better light extraction effect.
  • the preparation process of the compound of the present invention is simple and feasible, and the raw materials are readily available, which is suitable for mass production scale-up.
  • the compound is composed of a parent nucleus represented by formula (1) and one or two substituents represented by formula (H), and the substituent represented by formula (H) is substituted at any substitutable position of the parent nucleus represented by formula (1).
  • the X 1 and X 2 are independently selected from one of NR 3 , O or S, more preferably NR 3 .
  • the positions of X 1 and X 2 in the parent nucleus contain nitrogen atoms, and the boron atom has a resonance effect with the nitrogen atom in the same ring, so that this series of materials have narrow spectrum and thermal activation. The characteristic of delayed fluorescence emission, thereby further improving the device performance.
  • the parent nucleus shown in the formula (1) is specifically the structure shown in the formula (1-1);
  • the R 3 ′ has the same selection range as R 3 .
  • R 3 ' and R 3 can be selected from the same group or from different groups.
  • the compounds provided by the present invention include the following structures according to the different substitution sites of the (H) group:
  • substitution site is also arbitrary.
  • the ring D, ring G and ring F are independently selected from a substituted or unsubstituted C5-C30 aromatic ring or a substituted or unsubstituted C3-C30 heteroaromatic ring , preferably a substituted or unsubstituted C5-C14 aromatic ring, a substituted or unsubstituted C3-C14 heteroaromatic ring, more preferably a substituted or unsubstituted C5-C8 aromatic ring or a substituted or unsubstituted C5-C8 One of the heteroaromatic rings.
  • the ring D, ring G and ring F are independently selected from the groups represented by formula (b);
  • the ring D is connected to the rest of the parent core by sharing bonds c and d;
  • Ring G and Ring F are independently connected to other parts of the parent core through shared bond c or bond d;
  • the Z 1 , Z 2 , Z 3 and Z 4 are independently selected from CR 6 or N, and the R 6 is independently selected from hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, Amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl , one of C3-C60 heteroaryl groups, the R 6 is independently connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring. When there are two or more R 6 in formula (b), the two or more R 6 may be the same or different.
  • the parent nucleus represented by the formula (1) is specifically represented by the formula (1-1-1), the formula (1-1-2) or the formula (1-1-3).
  • the Z 1 , Z 1 ′, Z 1 ′′, Z 2 , Z 2 ′, Z 2 ′′, Z 3 , Z 3 ′, Z 3 ′′, Z 4 and Z 4 ′ are independently selected from CR 6 or N
  • the R 6 is independently selected from hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silane one of C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C60 aryl group, C3-C60 heteroaryl group, the R 6 is independently connected to the connected aromatic ring or heteroaromatic ring Connected into a ring or not connected into a ring;
  • Said Z 5 , Z 5 ', Z 6 , Z 6 ', Z 7 , Z 7 ', Z 8 and Z 8 ' are independently selected from CR 7 or N, and said R 7 is independently selected from hydrogen, halogen, Cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 One of heteroarylamino, C6-C60 aryl, C3-C60 heteroaryl, the R 7 is independently connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring; when the parent nucleus When there are two or more R 7 in , these two or more R 7 may be the same or different;
  • the R 3 has the same selection range as in formula (1), and the R 3 ′ has the same selection range as R 3 .
  • At most two of the Z 5 , Z 6 , Z 7 and Z 8 are N, and/or the Z 5 ′, Z 6 ′, Z 7 ′ and Z At most two of the 8 ' are N.
  • the R 3 is selected from one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, preferably substituted or unsubstituted C6 ⁇ C30 aryl; further preferably substituted or unsubstituted phenyl.
  • the substituted group is selected from any one or a combination of at least two of C1-C20 chain alkyl groups or C6-C60 aryl groups, preferably methyl, Any one of isopropyl, tert-butyl, and phenyl, or a combination of at least two of them.
  • the substituent represented by the formula (H) is specifically the structure represented by the formula (H');
  • m and n are independently an integer of 0 to 5, such as 1, 2, 3, or 4, etc., and r and s are each independently an integer of 0 to 6, such as 1, 2, 3 , 4 or 5, etc.; exemplarily, when m or n is 0, it is a three-membered ring, 1 is a four-membered ring, 2 is a five-membered ring, and so on;
  • R a and R b are independently selected from halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 A kind of alkoxy group, C1-C20 silyl group, C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C60 aryl group, C3-C60 heteroaryl group, the R a and R b are independent The ground is connected to the connected aliphatic ring to form a ring or not to form a ring.
  • R a When there are two or more R a in formula (H'), the two or more R a may be the same or different, and the same is true for R b .
  • the substituent represented by the formula (H) is specifically one of the structures represented by the formula (H-1) to the formula (H-6), preferably the formula (H- 1) The structure shown;
  • * represents the connecting bond of the group; wherein, the drawing of a straight line passing through two rings in (H-2), (H-4) and (H-6) represents that the connecting bond can be on any ring.
  • Ra , Rb , r and s all have the same selection range as in formula (H').
  • the R a and R b are independently selected from C1-C20 chain alkyl, preferably methyl or n-butyl.
  • the r and s are independently 0 to 2, such as 1, preferably 0.
  • the substituent represented by the formula (H) is specifically selected from one of the following groups:
  • * represents the connecting bond of the group.
  • any one of the structures described in M1-M104 can be exemplified;
  • the second object of the present invention is to provide an application of the compound described in one of the objects, and the compound is used in an organic electroluminescent device.
  • the blue electroluminescent device is preferably prepared from materials with an emission wavelength of ⁇ 500 nm, more preferably an emission wavelength of ⁇ 475 nm.
  • the compound is used as a light-emitting layer material, preferably a light-emitting dye, in the organic electroluminescent device.
  • the third object of the present invention is to provide an organic electroluminescence device, the organic electroluminescence device includes a substrate, and a first electrode, an organic layer and a second electrode sequentially formed on the substrate, the organic layer contains the compound described in one of the purposes.
  • the OLED device prepared by using the compound of the present invention has low start-up voltage and better service life, and can meet the requirements of current panel manufacturing enterprises for high-performance materials.
  • the organic layer includes a light-emitting layer, and the light-emitting layer contains the compound described in one of the purposes.
  • the OLED includes a first electrode and a second electrode, and an organic material layer between the electrodes.
  • the organic material can in turn be divided into multiple regions.
  • the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
  • a substrate may be used under the first electrode or over the second electrode.
  • the substrates are 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 as 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.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • SnO 2 tin dioxide
  • ZnO zinc oxide
  • magnesium Mg
  • silver (Ag) silver
  • Al aluminum
  • Al-lithium (Al-Li aluminum-lithium
  • Ca calcium
  • ytterbium (Yb) magnesium-indium
  • Mg-In magnesium-silver
  • Mg-Ag magnesium-silver
  • other metals or alloys and any combination between them.
  • the organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing and other methods.
  • the compound used as the organic material layer may be organic small molecules, organic macromolecules and polymers, and combinations thereof.
  • the hole transport region is located between the anode and the light emitting layer.
  • the hole transport region may 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 multi-layer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL between the HTL and the light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • the material of the hole transport region can 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-styrenesulfonate) (Pani/PSS), aromatic amine derivatives as shown below in HT-1 to HT-51; or any combination thereof.
  • phthalocyanine derivatives such as CuPc
  • conductive polymers or polymers containing conductive dopants such as polyphenylene vinylene, polyaniline/dodecylbenzenesulfonic acid (Pani /DBSA), poly(3,4-ethylene
  • the hole injection layer is located between the anode and the hole transport layer.
  • the hole injection layer may 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 use one or more compounds of 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 of the following HI-1-HI-3 compounds.
  • the light-emitting layer includes light-emitting dyes (ie dopant, dopant) that can emit different wavelength spectra, and may also include a host material (Host).
  • the light-emitting layer may be a monochromatic light-emitting layer that emits a single color such as red, green, and blue.
  • the monochromatic light-emitting layers of a plurality of different colors can be arranged in a plane according to a pixel pattern, or can be stacked together to form a colored light-emitting layer. When light-emitting layers of different colors are stacked together, they can be spaced from each other or connected to each other.
  • the light-emitting layer may 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 thermally activated delayed fluorescent light emitting 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 light of different colors.
  • the light-emitting layer adopts the technology of fluorescent electroluminescence.
  • the fluorescent host material of the light-emitting layer can be selected from, but not limited to, a combination of one or more of BFH-1 to BFH-17 listed below.
  • an electron blocking layer is located between the hole transport layer and the light emitting layer.
  • the electron blocking layer can use, but is not limited to, one or more compounds of the above-mentioned HT-1 to HT-51, or use, but not limited to, one or more compounds of the following PH-47 to PH-77; or Mixtures of one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 are employed, but not limited to.
  • the OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode.
  • the electron transport region may be an electron transport layer (ETL) with a single-layer structure, 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, a combination of one or more of ET-1 to ET-65 listed below.
  • a hole blocking layer is located between the electron transport layer and the light emitting layer.
  • the hole blocking layer can adopt, but is not limited to, one or more compounds of the above-mentioned ET-1 to ET-65, or adopt, but not limited to, one or more compounds of the following PH-1 to PH-46; Mixtures of one or more compounds of ET-1 to ET-65 and one or more of PH-1 to PH-46 may also be employed, but are not limited to.
  • the device may also include an electron injection layer between the electron transport layer and the cathode, and the material of the electron injection layer includes, but is not limited to, a combination of one or more of the following.
  • the fourth object of the present invention is to provide a display screen or display panel, in which the organic electroluminescent device as described in the third object is used; preferably, the display screen or display panel is an OLED monitor.
  • the fifth object of the present invention is to provide an electronic device, wherein the electronic device has the display screen or display panel described in the fourth object.
  • the present invention has the following beneficial effects:
  • a group containing a spiroalkane structure is introduced into the boron-containing compound, and this type of spiroalkane structure can effectively play a steric hindrance role and improve efficiency; in addition, this type of spiroalkane structure can effectively improve molecular transitions Dipole arrangement to achieve better light extraction effect, these points work together to achieve the technical advantage of improving device efficiency.
  • obtaining the compounds of the present invention is not limited to the synthetic methods and raw materials used in the present invention, and those skilled in the art can also select other methods or routes to obtain the compounds proposed by the present invention.
  • the compounds of the synthetic methods not mentioned in the present invention are all raw materials obtained through commercial channels, or are self-made according to known methods through these raw materials.
  • M17-4 (8.2g, 10mmol) was added into a 500mL there-necked flask, p-tert-butylbenzene (t-BuPh, 150mL) was added, the reaction system was cooled to 0°C after stirring for 20 minutes, and then 15mmol of tert-butyllithium was added. (t-BuLi), maintaining the low temperature and continuing to stir for 30 minutes. After that, the temperature was gradually increased to 60 °C, and the heating was continued for 3 h.
  • t-BuPh p-tert-butylbenzene
  • the synthesis scheme was the same as the synthesis of M17-3, 65 mmol of M17-2 was replaced by M17-1, and 12.7 g of white solid was obtained after column chromatography.
  • the synthesis scheme was the same as the synthesis of M-17, M17-4 was replaced by M69-4 (10 mmol), and purified to obtain 1.46 g of a yellow solid with a purity of 99.78%.
  • the glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreasing in an acetone:ethanol mixed solvent, baked in a clean environment until the water was completely removed, and UV light was used. Light and ozone cleaning, and bombarding the surface with a beam of low-energy cations;
  • the above-mentioned glass substrate with anode is placed in a vacuum chamber, evacuated to ⁇ 1 ⁇ 10 -5 Pa, and 10nm of HT-4:HI-3 (97 nm) is vacuum thermally evaporated on the above-mentioned anode layer film in sequence.
  • Device Example 2 to Device Example 21 were fabricated by the same method as Device Example 1, except that the dye M-1 in the light-emitting layer was replaced respectively, and other parameters remained unchanged, see Table 1 for details.
  • Device Comparative Example 1 to Device Comparative Example 2 were fabricated by the same method as Device Example 1, except that the dye M-1 in the light-emitting layer was replaced by ref-1 and ref-2 respectively (refer to CN110662750A for the compound acquisition method).
  • the driving voltage and external quantum efficiency of the organic electroluminescent devices prepared in the above device examples and device comparative examples were measured using a digital source meter and PR650. Specifically, the voltage is increased at a rate of 0.1V per second , and the voltage when the brightness of the organic electroluminescent device reaches 1000cd/m2 is determined as the driving voltage at the corresponding brightness. At the same time, the device can be directly tested on PR650. External quantum efficiency (EQE%);
  • the novel organic material of the present invention is used in organic electroluminescence devices.
  • the example device 1-21 can effectively reduce the operating voltage and improve the external quantum efficiency, and is a blue light with good performance. Material.
  • the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

The present invention relates to a compound and an application thereof. The compound consists of a parent nucleus represented by formula (1) and at least one substituent represented by formula (H), and the substituent represented by formula (H) is substituted at any substitutable position of the parent nucleus represented by formula (1). By introducing a type of groups containing spiroalkane structures into a boron-containing parent nucleus, this type of spiroalkane structures can effectively achieve a steric hindrance effect, thereby improving efficiency. In addition, this type of spiroalkane structures can effectively improve the molecular transition dipole arrangement, thereby achieving a better light extraction effect. Under the combined action of the foregoing effects, the technical advantage of improving device efficiency is realized.

Description

一种化合物及其应用A compound and its application 技术领域technical field
本发明涉及有机电致发光技术领域，尤其涉及一种化合物及其应用。The present invention relates to the technical field of organic electroluminescence, in particular to a compound and its application.
背景技术Background technique
人们获取信息的主要途径是通过视觉来实现的，因此在人类同信息交互的过程中，显示装置至关重要。有机电致发光二极管(OLEDs)具有可柔性、自发光、高对比度、大尺寸、低功耗等诸多优点而成为了目前主流的显示装置之一。The main way for people to obtain information is through vision, so in the process of human interaction with information, display devices are very important. Organic electroluminescent diodes (OLEDs) have many advantages such as flexibility, self-luminescence, high contrast, large size, and low power consumption, and have become one of the mainstream display devices.
其中作为三基色的红光以及绿光染料，由于一般含有重原子如Ir、Pt等，理论上能够实现100％的内量子效率，电致发光效率较高，功耗低，成为了目前商业化显示设备的主流。然而，蓝色磷光材料的色度以及寿命都达不到目前商业化的显示需求。目前，蓝光器件仍然采用传统荧光材料来实现高的色纯度以及长的器件寿命。Among them, red and green dyes, which are three primary colors, generally contain heavy atoms such as Ir, Pt, etc., can theoretically achieve 100% internal quantum efficiency, high electroluminescence efficiency, and low power consumption. Mainstream display devices. However, the chromaticity and lifetime of blue phosphorescent materials cannot meet the current commercial display requirements. At present, blue light devices still use traditional fluorescent materials to achieve high color purity and long device lifetime.
现有的有机电致发光材料在发光性能方面还有很大的改进余地，业界亟需开发新的发光材料体系以满足商业化需求。Existing organic electroluminescent materials still have a lot of room for improvement in terms of luminescent properties, and the industry urgently needs to develop new luminescent material systems to meet commercialization needs.
CN110662750A公开了一类含硼有机材料，该篇专利中，优选取了环己烷作为位阻基团使用，主要目的是降低器件中的浓度淬灭。但是应用该有机材料的有机电致发光器件的性能仍有待提升。CN110662750A discloses a class of boron-containing organic materials. In this patent, cyclohexane is preferably used as a steric hindrance group, and the main purpose is to reduce the concentration quenching in the device. However, the performance of organic electroluminescent devices using this organic material still needs to be improved.
因此，本领域亟待开发一种新型的蓝光有机电致发光材料，进一步提升器件性能。Therefore, there is an urgent need in the art to develop a new type of blue-light organic electroluminescent material to further improve device performance.
发明内容SUMMARY OF THE INVENTION
本发明的目的之一在于提供一种化合物，尤其在于提供一种含硼类化合物，是一种蓝光荧光材料，所述化合物应用与有机电致发光器件时，能够提高器件性能，降低驱动电压，提高器件效率。One of the objectives of the present invention is to provide a compound, especially a boron-containing compound, which is a blue fluorescent material. When the compound is applied to an organic electroluminescence device, the device performance can be improved and the driving voltage can be reduced. Improve device efficiency.
为达此目的，本发明采用以下技术方案：For this purpose, the present invention adopts the following technical solutions:
本发明提供一种化合物，所述化合物由式(1)所示的母核以及至少一个(例如1个、2个、3个、4个、5个或6个等)式(H)所示的取代基组成，且式(H)所示的取代基取代在式(1)所示的母核的任意可取代位置；The present invention provides a compound represented by a parent nucleus represented by formula (1) and at least one (eg 1, 2, 3, 4, 5 or 6, etc.) represented by formula (H) and the substituent shown in formula (H) is substituted at any substitutable position of the parent nucleus shown in formula (1);
Figure PCTCN2021114065-appb-000001
Figure PCTCN2021114065-appb-000001
其中，*代表基团的连接键；Wherein, * represents the connecting bond of the group;
式(1)中，所述环D、环G和环F独立地选自取代或未取代的C5～C60芳环或 者取代或未取代的C3～C60杂芳环中的一种，所述取代的基团与相连接的芳环或杂芳环连接成环或不连接成环；所述“连接成环或不连接成环”指的是当C6～C60芳环或C3～C60杂芳环上含有取代基时，该取代基可以与被取代的芳环或杂芳环连接形成环结构，也可以只是以单键取代的方式取代在芳环或杂芳环上，其中连接成环的方式不做具体限定，示例性地可以是通过单键连接，也可以是通过亚甲基等连接基团连接，下文涉及相似的表达方式时，均具有同样的意义，不一一赘述；In formula (1), the ring D, ring G and ring F are independently selected from a substituted or unsubstituted C5-C60 aromatic ring or a substituted or unsubstituted C3-C60 heteroaromatic ring, the substituted or unsubstituted C3-C60 heteroaromatic ring. The group is connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring; the "connected to form a ring or not to form a ring" refers to when a C6-C60 aromatic ring or a C3-C60 heteroaromatic ring When there is a substituent on it, the substituent can be connected with the substituted aromatic ring or heteroaromatic ring to form a ring structure, or it can be substituted on the aromatic ring or heteroaromatic ring only by single bond substitution, wherein the way of connecting into a ring Without specific limitation, it can be exemplarily connected by a single bond, or it can be connected by a connecting group such as a methylene group. When referring to similar expressions below, they all have the same meaning and will not be repeated one by one;
式(1)中，所述X 1和X 2独立地选自CR 1R 2、NR 3、O、S或SiR 4R 5中的一种，所述R 1、R 2、R 3、R 4和R 5独立地与相邻的环D、环G或环F连接成环或不连接成环；当化合物中同时存在两个R 3时，这两个R 3可以选自相同的基团，也可以选自不同的基团，R 1、R 2、R 4和R 5同理； In formula (1), the X 1 and X 2 are independently selected from one of CR 1 R 2 , NR 3 , O, S or SiR 4 R 5 , the R 1 , R 2 , R 3 , R 5 4 and R 5 are independently connected to the adjacent ring D, ring G or ring F to form a ring or not to form a ring; when there are two R 3 in the compound at the same time, the two R 3 can be selected from the same group , can also be selected from different groups, R 1 , R 2 , R 4 and R 5 are the same;
所述R 1、R 2、R 3、R 4和R 5独立地选自取代或未取代的C1～C20链状烷基、取代或未取代的C3～C20环烷基、取代或未取代的C6～C60芳基、取代或未取代的C3～C60杂芳基中的一种，所述取代的基团与相连接的芳环或杂芳环连接成环或不连接成环； The R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 cycloalkyl One of C6-C60 aryl group, substituted or unsubstituted C3-C60 heteroaryl group, the substituted group is connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring;
式(H)中，所述环A和环E独立地选自取代或未取代的C3～C8脂肪环，所述取代的基团与相连接的脂肪环连接成环或不连接成环；所述“C3～C8”指的是脂肪环含有3～8的碳原子，该数目包括环A和环E共享的碳原子；In formula (H), the ring A and ring E are independently selected from substituted or unsubstituted C3-C8 aliphatic rings, and the substituted group is connected to the connected aliphatic ring to form a ring or not to form a ring; the The above-mentioned "C3-C8" means that the aliphatic ring contains 3-8 carbon atoms, and the number includes the carbon atoms shared by ring A and ring E;
式(H)中，所述环A和环E通过共用一个sp3杂化的C原子进行连接；共用一个sp3杂化的C原子进行连接，即形成螺环结构；In formula (H), the ring A and the ring E are connected by sharing a sp3 hybridized C atom; sharing a sp3 hybridized C atom for connection, that is, a spiro ring structure is formed;
环D、环G、环F、R 1、R 2、R 3、R 4、R 5、环A和环E中，所述取代的基团独立地选自卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种或者至少两种的组合。 In Ring D, Ring G, Ring F, R 1 , R 2 , R 3 , R 4 , R 5 , Ring A and Ring E, the substituted groups are independently selected from halogen, cyano, carbonyl, nitro , hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6- One or a combination of at least two C60 aryl groups and C3-C60 heteroaryl groups.
本发明中的芳环是指芳基的环状结构，具体例可以参考本说明书中的芳基部分。本发明中的杂芳环是指杂芳基的环状结构，具体例可以参考本说明书中的杂芳基部分。The aromatic ring in the present invention refers to the cyclic structure of an aryl group, and for a specific example, reference can be made to the aryl moiety in this specification. The heteroaromatic ring in the present invention refers to a cyclic structure of a heteroaryl group, and for specific examples, reference can be made to the heteroaryl group in this specification.
本发明中，“取代的基团”指的是“取代或未取代”的基团被取代时取代基的选择范围，个数不做具体限定，只要满足化合物键要求即可，示例性地，可以为1个、2个、3个、4个或5个，且当取代基的个数为2个及以上时，这2个及以上取代基可以相同也可以不同。In the present invention, "substituted group" refers to the selection range of the substituent when the "substituted or unsubstituted" group is substituted, and the number is not specifically limited, as long as it meets the requirements of compound bonds. There may be 1, 2, 3, 4 or 5, and when the number of substituents is 2 or more, the 2 or more substituents may be the same or different.
本发明中，式(1)所示的母核上取代有至少两个式(H)所示的取代基时，这至少两个取代基的结构可以相同，也可以不相同。In the present invention, when at least two substituents represented by formula (H) are substituted on the core represented by formula (1), the structures of the at least two substituents may be the same or different.
本发明中，卤素代表氯原子、氟原子、溴原子等。In the present invention, halogen represents a chlorine atom, a fluorine atom, a bromine atom or the like.
本发明中，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。In the present invention, the expressions of Ca-Cb represent that the number of carbon atoms of the group is a-b, unless otherwise specified, generally the number of carbon atoms does not include the number of carbon atoms of the substituent.
本发明中，“—”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。In the present invention, the expression of the ring structure crossed by "—" means that the connection site is at any position on the ring structure that can form a bond.
本说明书中，芳基包括单环芳基或稠环芳基，杂芳基包括单环杂芳基或稠环杂芳基。In this specification, the aryl group includes a monocyclic aryl group or a fused-ring aryl group, and the heteroaryl group includes a monocyclic heteroaryl group or a fused-ring heteroaryl group.
本发明中，C6(或C5)～C60(例如C8、C10、C12、C14、C16、C18、C20、C22、C24、C26、C28、C30、C32、C34、C36、C38、C40、C42、C44、C46、C48、C50、C52、C54、C56、C58等)芳基(或芳环)优选为取代或未取代的C6～C30芳基(芳环)，进一步优选为取代或未取代的C6～C20芳基(芳环)，更优选为由苯基、联苯基、三联苯基、萘基、蒽基、菲基、茚基、芴基及其衍生物、荧蒽基、三亚苯基、芘基、苝基、
Figure PCTCN2021114065-appb-000002
基和并四苯基所组成的组中的基团。具体地，联苯基选自2-联苯基、3-联苯基和4-联苯基；三联苯基包括对-三联苯基-4-基、对-三联苯基-3-基、对-三联苯 基-2-基、间-三联苯基-4-基、间-三联苯基-3-基和间-三联苯基-2-基；所述萘基包括1-萘基和2-萘基；蒽基选自1-蒽基、2-蒽基和9-蒽基；所述芴基选自1-芴基、2-芴基、3-芴基、4-芴基和9-芴基；所述芴基衍生物选自9,9’-二甲基芴、9,9’-螺二芴和苯并芴；所述芘基选自1-芘基、2-芘基和4-芘基；并四苯基选自1-并四苯基、2-并四苯基和9-并四苯基。 In the present invention, C6 (or C5) to C60 (such as C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44 , C46, C48, C50, C52, C54, C56, C58, etc.) aryl (or aromatic ring) is preferably a substituted or unsubstituted C6-C30 aryl (aromatic ring), more preferably a substituted or unsubstituted C6- C20 aryl group (aromatic ring), more preferably a group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl and derivatives thereof, fluoranthene, triphenylene, Pyrene, perylene,
Figure PCTCN2021114065-appb-000002
A group in the group consisting of radical and naphthacyl. Specifically, biphenyl is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl groups include 1-naphthyl and 2-naphthyl; anthracenyl is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene; the pyrenyl is selected from 1-pyrenyl, 2-pyrene and 4-pyrenyl; naphthacyl is selected from 1-naphthacyl, 2-naphthacyl and 9-naphthacyl.
本发明中，C6～C60芳基氨基代表C6～C60芳基与氨基通过单键连接而成的基团，其中的C6～C60芳基同上段所述。In the present invention, the C6-C60 arylamino group represents a group formed by connecting a C6-C60 aryl group and an amino group through a single bond, wherein the C6-C60 aryl group is as described in the previous paragraph.
本发明中所述的杂原子，通常指选自N、O、S、P、Si和Se中的原子或原子团，优选选自N、O、S。本发明中所述的原子名称，包括其对应的各种同位素，例如，氢(H)则包括 1H(氕或作H)、 2H(氘或作D)等；碳(C)则包括 12C、 13C等。 The heteroatoms mentioned in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, preferably selected from N, O, S. The atom names described in the present invention include their corresponding isotopes, for example, hydrogen (H) includes 1 H (protium or H), 2 H (deuterium or D), etc.; carbon (C) includes 12C , 13C , etc.
本发明中，C3～C60(例如C4、C5、C6、C8、C10、C12、C14、C16、C18、C20、C22、C24、C26、C28、C30、C32、C34、C36、C38、C40、C42、C44、C46、C48、C50、C52、C54、C56、C58等)杂芳基(杂芳环)优选为C3～C30杂芳基(杂芳环)，进一步优选为C4～C20杂芳基(杂芳环)，更优选为含氮杂芳基、含氧杂芳基、含硫杂芳基等，具体的例子可举出：呋喃基、噻吩基、吡咯基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基及其衍生物，其中，所述咔唑基衍生物优选为9-苯基咔唑、9-萘基咔唑苯并咔唑、二苯并咔唑、或吲哚并咔唑。In the present invention, C3 to C60 (such as C4, C5, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42 , C44, C46, C48, C50, C52, C54, C56, C58, etc.) heteroaryl (heteroaryl ring) is preferably C3～C30 heteroaryl (heteroaryl ring), more preferably C4～C20 heteroaryl ( heteroaromatic ring), more preferably nitrogen-containing heteroaryl, oxygen-containing heteroaryl, sulfur-containing heteroaryl, etc. Specific examples include: furyl, thienyl, pyrrolyl, benzofuranyl, benzofuran Thienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole , 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolocarbazole.
本发明中，C3～C60杂芳基代表C3～C60杂芳基与氨基通过单键连接而成的基团，其中的C3～C60杂芳基同上段所述。In the present invention, the C3-C60 heteroaryl group represents a group formed by connecting a C3-C60 heteroaryl group and an amino group through a single bond, wherein the C3-C60 heteroaryl group is the same as that described in the previous paragraph.
本发明中，上述C1～C20链状烷基优选为C1～C10的链状烷基，更优选为C1～C6的链状烷基，例如可举出：甲基、乙基、正丙基、正丁基、正己基、正辛基、异丙基、异丁基、叔丁基等。In the present invention, the above-mentioned C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, more preferably a C1-C6 chain alkyl group, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, tert-butyl, etc.
本说明书中，C3～C20环烷基包括单环烷基和多环烷基，其中多环烷基指的是含有至少两个环结构的烷基。In this specification, C3-C20 cycloalkyl includes monocycloalkyl and polycycloalkyl, wherein polycycloalkyl refers to an alkyl group containing at least two ring structures.
本发明中，C3～C20环烷基优选为C3～C12环烷基，进一步优选为C3-C10的环烷基，例如可举出：环丙基、环丁基、环戊基、环己基、环庚基等。In the present invention, the C3-C20 cycloalkyl group is preferably a C3-C12 cycloalkyl group, more preferably a C3-C10 cycloalkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Cycloheptyl etc.
本发明中，C1～C20烷氧基优选为C1～C10烷氧基，更优选C1～C6烷氧基，例如可举出：甲氧基、乙氧基等。In the present invention, the C1-C20 alkoxy group is preferably a C1-C10 alkoxy group, more preferably a C1-C6 alkoxy group, and examples thereof include a methoxy group and an ethoxy group.
本发明中，C1～C20硅烷基优选为C1～C10硅烷基，更优选C1～C6硅烷基，例如可举出甲基硅烷、乙基硅烷、异丙基硅烷、叔丁基硅烷、苯基硅烷等。In the present invention, the C1-C20 silyl group is preferably a C1-C10 silyl group, more preferably a C1-C6 silyl group, and examples thereof include methylsilane, ethylsilane, isopropylsilane, tert-butylsilane, and phenylsilane. Wait.
本发明提供了一种新型的含硼化合物，在含硼母核中引入一类含有螺烷烃结构的基团，这类螺烷烃结构可以有效的起到位阻作用，提升效率；另外这类螺烷烃结构，可以有效的改善分子跃迁偶极排列，实现更好的光取出效果，这几点共同作用，实现器件效率提升的技术优势。The present invention provides a new type of boron-containing compound. A group containing a spiroalkane structure is introduced into the boron-containing parent core, and the spiroalkane structure can effectively play a steric hindrance role and improve efficiency; The structure can effectively improve the molecular transition dipole arrangement and achieve better light extraction effect. These points work together to achieve the technical advantage of improving device efficiency.
此外，本发明化合物的制备工艺简单易行，原料易得，适合于量产放大。In addition, the preparation process of the compound of the present invention is simple and feasible, and the raw materials are readily available, which is suitable for mass production scale-up.
在本发明中的一个实施方式中，所述化合物由式(1)所示的母核以及一个或两个式(H)所示的取代基组成，且式(H)所示的取代基取代在式(1)所示的母核的任意可取代位置。In one embodiment of the present invention, the compound is composed of a parent nucleus represented by formula (1) and one or two substituents represented by formula (H), and the substituent represented by formula (H) is substituted at any substitutable position of the parent nucleus represented by formula (1).
在本发明中的一个实施方式中，所述X 1和X 2独立地选自NR 3、O或S中的一种，进一步优选NR 3。 In one embodiment of the present invention, the X 1 and X 2 are independently selected from one of NR 3 , O or S, more preferably NR 3 .
在本发明中的一个实施方式中，优选母核中X 1和X 2的位置含有氮原子，硼原子与同一环内的氮原子具有共振效应，因而使这一系列材料具备窄光谱以及热活化延迟荧光发射的特点，从而进一步提高器件性能。 In one embodiment of the present invention, it is preferred that the positions of X 1 and X 2 in the parent nucleus contain nitrogen atoms, and the boron atom has a resonance effect with the nitrogen atom in the same ring, so that this series of materials have narrow spectrum and thermal activation. The characteristic of delayed fluorescence emission, thereby further improving the device performance.
在本发明中的一个实施方式中，所述式(1)所示的母核具体为式(1-1)所示的 结构；In one embodiment of the present invention, the parent nucleus shown in the formula (1) is specifically the structure shown in the formula (1-1);
Figure PCTCN2021114065-appb-000003
Figure PCTCN2021114065-appb-000003
式(1-1)中，所述环D、环G、环F和R 3均具有与式(1)中相同的选择范围； In formula (1-1), the ring D, ring G, ring F and R 3 all have the same selection range as in formula (1);
所述R 3'具有与R 3相同的选择范围。R 3'与R 3可以选择相同的基团，也可以选自不同的基团。 The R 3 ′ has the same selection range as R 3 . R 3 ' and R 3 can be selected from the same group or from different groups.
本发明提供的化合物根据(H)基团取代位点的不同包括如下结构：The compounds provided by the present invention include the following structures according to the different substitution sites of the (H) group:
Figure PCTCN2021114065-appb-000004
Figure PCTCN2021114065-appb-000004
当(H)基团取代在R 3上时，取代位点也是任意的。 When the (H) group is substituted on R3 , the substitution site is also arbitrary.
在本发明中的一个实施方式中，所述环D、环G和环F独立地选自取代或未取代的C5～C30芳环或者取代或未取代的C3～C30杂芳环中的一种，优选取代或未取代的C5～C14芳环、取代或未取代的C3～C14杂芳环中的一种，进一步优选取代或未取代的C5～C8芳环或者取代或未取代的C5～C8杂芳环中的一种。In one embodiment of the present invention, the ring D, ring G and ring F are independently selected from a substituted or unsubstituted C5-C30 aromatic ring or a substituted or unsubstituted C3-C30 heteroaromatic ring , preferably a substituted or unsubstituted C5-C14 aromatic ring, a substituted or unsubstituted C3-C14 heteroaromatic ring, more preferably a substituted or unsubstituted C5-C8 aromatic ring or a substituted or unsubstituted C5-C8 One of the heteroaromatic rings.
在本发明中的一个实施方式中，所述环D、环G和环F独立地选自式(b)所示的基团；In one embodiment of the present invention, the ring D, ring G and ring F are independently selected from the groups represented by formula (b);
Figure PCTCN2021114065-appb-000005
Figure PCTCN2021114065-appb-000005
所述环D通过共享化学键c和化学键d与母核的其他部分连接；The ring D is connected to the rest of the parent core by sharing bonds c and d;
所述环G和环F独立地通过共享化学键c或化学键d与母核的其他部分连接；Said Ring G and Ring F are independently connected to other parts of the parent core through shared bond c or bond d;
式(b)中，所述Z 1、Z 2、Z 3和Z 4独立地选自CR 6或N，所述R 6独立地选自氢、卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R 6独立地与相连接的芳环或杂芳环连接成环或不连接成环。当式(b)中存在两个及以上R 6时，这两个及以上R 6可以相同也可以不同。 In formula (b), the Z 1 , Z 2 , Z 3 and Z 4 are independently selected from CR 6 or N, and the R 6 is independently selected from hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, Amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl , one of C3-C60 heteroaryl groups, the R 6 is independently connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring. When there are two or more R 6 in formula (b), the two or more R 6 may be the same or different.
在本发明中的一个实施方式中，所述式(1)所示的母核具体为式(1-1-1)、式(1-1-2)或式(1-1-3)所示的结构，优选式(1-1-1)所示的结构；In one embodiment of the present invention, the parent nucleus represented by the formula (1) is specifically represented by the formula (1-1-1), the formula (1-1-2) or the formula (1-1-3). The structure shown, preferably the structure shown in formula (1-1-1);
Figure PCTCN2021114065-appb-000006
Figure PCTCN2021114065-appb-000006
所述Z 1、Z 1'、Z 1”、Z 2、Z 2'、Z 2”、Z 3、Z 3'、Z 3”、Z 4和Z 4'独立地选自CR 6或N，所述R 6独立地选自氢、卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、 C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R 6独立地与相连接的芳环或杂芳环连接成环或不连接成环； The Z 1 , Z 1 ′, Z 1 ″, Z 2 , Z 2 ′, Z 2 ″, Z 3 , Z 3 ′, Z 3 ″, Z 4 and Z 4 ′ are independently selected from CR 6 or N, The R 6 is independently selected from hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silane one of C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C60 aryl group, C3-C60 heteroaryl group, the R 6 is independently connected to the connected aromatic ring or heteroaromatic ring Connected into a ring or not connected into a ring;
所述Z 5、Z 5'、Z 6、Z 6'、Z 7、Z 7'、Z 8和Z 8'独立地选自CR 7或N，所述R 7独立地选自氢、卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R 7独立地与相连接的芳环或杂芳环连接成环或不连接成环；当母核中存在两个及以上R 7时，这两个及以上R 7可以相同也可以不同； Said Z 5 , Z 5 ', Z 6 , Z 6 ', Z 7 , Z 7 ', Z 8 and Z 8 ' are independently selected from CR 7 or N, and said R 7 is independently selected from hydrogen, halogen, Cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 One of heteroarylamino, C6-C60 aryl, C3-C60 heteroaryl, the R 7 is independently connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring; when the parent nucleus When there are two or more R 7 in , these two or more R 7 may be the same or different;
所述R 3具有与式(1)中相同的选择范围，所述R 3'具有与R 3相同的选择范围。 The R 3 has the same selection range as in formula (1), and the R 3 ′ has the same selection range as R 3 .
在本发明中的一个实施方式中，所述Z 5、Z 6、Z 7和Z 8中至多有两个为N，和/或，所述Z 5'、Z 6'、Z 7'和Z 8'中至多有两个为N。 In one embodiment of the present invention, at most two of the Z 5 , Z 6 , Z 7 and Z 8 are N, and/or the Z 5 ′, Z 6 ′, Z 7 ′ and Z At most two of the 8 ' are N.
在本发明中的一个实施方式中，所述R 3选自取代或未取代的C6～C60芳基、取代或未取代的C3～C60杂芳基中的一种，优选取代或未取代的C6～C30芳基；进一步优选取代或未取代的苯基。 In one embodiment of the present invention, the R 3 is selected from one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, preferably substituted or unsubstituted C6 ~C30 aryl; further preferably substituted or unsubstituted phenyl.
在本发明中的一个实施方式中，R 3中，所述取代的基团选自C1～C20链状烷基或C6～C60芳基中的任意一种或至少两种组合，优选甲基、异丙基、叔丁基、苯基中的任意一种或至少两种组合。 In one embodiment of the present invention, in R 3 , the substituted group is selected from any one or a combination of at least two of C1-C20 chain alkyl groups or C6-C60 aryl groups, preferably methyl, Any one of isopropyl, tert-butyl, and phenyl, or a combination of at least two of them.
在本发明中的一个实施方式中，所述式(H)所示的取代基具体为式(H')所示的结构；In one embodiment of the present invention, the substituent represented by the formula (H) is specifically the structure represented by the formula (H');
Figure PCTCN2021114065-appb-000007
Figure PCTCN2021114065-appb-000007
式(H')中，*代表基团的连接键；In formula (H'), * represents the connecting bond of the group;
式(H')中，所述m和n独立地为0～5的整数，例如1、2、3或4等，r和s各自独立地为0～6的整数，例如1、2、3、4或5等；示例性地，当m或n取0时，为三元环，取1为四元环，取2为五元环，以此类推；In formula (H'), m and n are independently an integer of 0 to 5, such as 1, 2, 3, or 4, etc., and r and s are each independently an integer of 0 to 6, such as 1, 2, 3 , 4 or 5, etc.; exemplarily, when m or n is 0, it is a three-membered ring, 1 is a four-membered ring, 2 is a five-membered ring, and so on;
式(H')中，所述R a和R b独立地选自卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R a和R b独立地与相连接的脂肪环连接成环或不连接成环。 In formula (H'), R a and R b are independently selected from halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 A kind of alkoxy group, C1-C20 silyl group, C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C60 aryl group, C3-C60 heteroaryl group, the R a and R b are independent The ground is connected to the connected aliphatic ring to form a ring or not to form a ring.
当式(H')中存在两个及以上R a时，这两个及以上R a可以相同也可以不同，R b同理。 When there are two or more R a in formula (H'), the two or more R a may be the same or different, and the same is true for R b .
在本发明中的一个实施方式中，所述式(H)所示的取代基具体为式(H-1)至式(H-6)所示的结构中的一种，优选式(H-1)所示的结构；In one embodiment of the present invention, the substituent represented by the formula (H) is specifically one of the structures represented by the formula (H-1) to the formula (H-6), preferably the formula (H- 1) The structure shown;
Figure PCTCN2021114065-appb-000008
Figure PCTCN2021114065-appb-000008
其中，*代表基团的连接键；其中，(H-2)、(H-4)和(H-6)中直线穿过两个环的画法代表连接键可以在任意一个环上。Wherein, * represents the connecting bond of the group; wherein, the drawing of a straight line passing through two rings in (H-2), (H-4) and (H-6) represents that the connecting bond can be on any ring.
所述R a、R b、r和s均具有与式(H')中相同的选择范围。 Said Ra , Rb , r and s all have the same selection range as in formula (H').
在本发明中的一个实施方式中，所述R a和R b独立地选自C1～C20链状烷基，优选甲基或正丁基。 In one embodiment of the present invention, the R a and R b are independently selected from C1-C20 chain alkyl, preferably methyl or n-butyl.
在本发明中的一个实施方式中，所述r和s的独立地为0～2，例如1，优选为0。In one embodiment of the present invention, the r and s are independently 0 to 2, such as 1, preferably 0.
在本发明中的一个实施方式中，所述式(H)所示的取代基具体选自如下基团中的一种：In one embodiment of the present invention, the substituent represented by the formula (H) is specifically selected from one of the following groups:
Figure PCTCN2021114065-appb-000009
Figure PCTCN2021114065-appb-000009
其中，*代表基团的连接键。Wherein, * represents the connecting bond of the group.
作为在本发明中的具体实施方式，可以例举具有M1-M104所述的结构中的任意一种；As a specific embodiment in the present invention, any one of the structures described in M1-M104 can be exemplified;
Figure PCTCN2021114065-appb-000010
Figure PCTCN2021114065-appb-000010
Figure PCTCN2021114065-appb-000011
Figure PCTCN2021114065-appb-000011
Figure PCTCN2021114065-appb-000012
Figure PCTCN2021114065-appb-000012
Figure PCTCN2021114065-appb-000013
Figure PCTCN2021114065-appb-000013
Figure PCTCN2021114065-appb-000014
Figure PCTCN2021114065-appb-000014
本发明的目的之二在于提供一种目的之一所述的化合物的应用，所述化合物用于有机电致发光器件。The second object of the present invention is to provide an application of the compound described in one of the objects, and the compound is used in an organic electroluminescent device.
优选发射波长≤500nm，更优选发射波长≤475nm的材料制备蓝光电致发光器件。The blue electroluminescent device is preferably prepared from materials with an emission wavelength of ≤ 500 nm, more preferably an emission wavelength of ≤ 475 nm.
在本发明中的一个实施方式中，所述化合物在所述有机电致发光器件中作为发光层材料，优选作为发光染料。In one embodiment of the present invention, the compound is used as a light-emitting layer material, preferably a light-emitting dye, in the organic electroluminescent device.
本发明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基板，以及依次形成在所述基板上的第一电极、有机层和第二电极，所述有机层中含有目的之一述的化合物。The third object of the present invention is to provide an organic electroluminescence device, the organic electroluminescence device includes a substrate, and a first electrode, an organic layer and a second electrode sequentially formed on the substrate, the organic layer contains the compound described in one of the purposes.
采用本发明化合物制备的OLED器件具有低启动电压、更优的使用寿命，能够满足当前面板制造企业对高性能材料的要求。The OLED device prepared by using the compound of the present invention has low start-up voltage and better service life, and can meet the requirements of current panel manufacturing enterprises for high-performance materials.
在本发明中的一个实施方式中，所述有机层包括发光层，所述发光层中含有目的之一所述的化合物。In one embodiment of the present invention, the organic layer includes a light-emitting layer, and the light-emitting layer contains the compound described in one of the purposes.
OLED包括位于第一电极和第二电极，以及位于电极之间的有机材料层。该有机材料又可以分为多个区域。比如，该有机材料层可以包括空穴传输区、发光层、电子传输区。The OLED includes a first electrode and a second electrode, and an organic material layer between the electrodes. The organic material can in turn be divided into multiple regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
在具体实施例中，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)。In particular embodiments, a substrate may be used under the first electrode or over the second electrode. The substrates are glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. In addition, a thin film transistor (TFT) may be provided on a substrate as a display.
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。 The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, 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. When the first electrode is used as a cathode, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In) can be used ), magnesium-silver (Mg-Ag) and other metals or alloys, and any combination between them.
有机材料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。用作有机材料层的化合物可以为有机小分子、有机大分子和聚合物，以及它们的组合。The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing and other methods. The compound used as the organic material layer may be organic small molecules, organic macromolecules and polymers, and combinations thereof.
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。The hole transport region is located between the anode and the light emitting layer. The hole transport region may 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 multi-layer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL between the HTL and the light-emitting layer.
空穴传输区的材料可以选自、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)、如下面HT-1至HT-51所示的芳香胺衍生物；或者其任意组合。The material of the hole transport region can 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-styrenesulfonate) (Pani/PSS), aromatic amine derivatives as shown below in HT-1 to HT-51; or any combination thereof.
Figure PCTCN2021114065-appb-000015
Figure PCTCN2021114065-appb-000015
Figure PCTCN2021114065-appb-000016
Figure PCTCN2021114065-appb-000016
Figure PCTCN2021114065-appb-000017
Figure PCTCN2021114065-appb-000017
Figure PCTCN2021114065-appb-000018
Figure PCTCN2021114065-appb-000018
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。The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of the above-mentioned HT-1 to HT-51, or use one or more compounds of 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 of the following HI-1-HI-3 compounds.
Figure PCTCN2021114065-appb-000019
Figure PCTCN2021114065-appb-000019
发光层包括可以发射不同波长光谱的的发光染料(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。The light-emitting layer includes light-emitting dyes (ie dopant, dopant) that can emit different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochromatic light-emitting layer that emits a single color such as red, green, and blue. The monochromatic light-emitting layers of a plurality of different colors can be arranged in a plane according to a pixel pattern, or can be stacked together to form a colored light-emitting layer. When light-emitting layers of different colors are stacked together, they can be spaced from each other or connected to each other. The light-emitting layer may also be a single-color light-emitting layer capable of simultaneously emitting different colors such as red, green, and blue.
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。According to different technologies, different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent light emitting materials can be used as materials for the light emitting layer. In an OLED device, 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 light of different colors.
在本发明的一方面，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、但不限于以下所罗列的BFH-1至BFH-17的一种或多种的组合。In one aspect of the present invention, the light-emitting layer adopts the technology of fluorescent electroluminescence. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, a combination of one or more of BFH-1 to BFH-17 listed below.
Figure PCTCN2021114065-appb-000020
Figure PCTCN2021114065-appb-000020
本发明的一方面，电子阻挡层(EBL)位于空穴传输层与发光层之间。电子阻挡层可以采用、但不限于上述HT-1至HT-51的一种或多种化合物，或者采用、但不限于下述PH-47至PH-77的一种或多种化合物；也可以采用、但不限于HT-1至HT-51的一种或多种化合物和PH-47至PH-77的一种或多种化合物的混合物。In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer can use, but is not limited to, one or more compounds of the above-mentioned HT-1 to HT-51, or use, but not limited to, one or more compounds of the following PH-47 to PH-77; or Mixtures of one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 are employed, but not limited to.
Figure PCTCN2021114065-appb-000021
Figure PCTCN2021114065-appb-000021
Figure PCTCN2021114065-appb-000022
Figure PCTCN2021114065-appb-000022
Figure PCTCN2021114065-appb-000023
Figure PCTCN2021114065-appb-000023
OLED有机材料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。The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be an electron transport layer (ETL) with a single-layer structure, 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).
本发明的一方面，电子传输层材料可以选自、但不限于以下所罗列的ET-1至ET-65的一种或多种的组合。In one aspect of the present invention, the electron transport layer material may be selected from, but not limited to, a combination of one or more of ET-1 to ET-65 listed below.
Figure PCTCN2021114065-appb-000024
Figure PCTCN2021114065-appb-000024
Figure PCTCN2021114065-appb-000025
Figure PCTCN2021114065-appb-000025
Figure PCTCN2021114065-appb-000026
Figure PCTCN2021114065-appb-000026
Figure PCTCN2021114065-appb-000027
Figure PCTCN2021114065-appb-000027
本发明的一方面，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-65的一种或多种化合物，或者采用、但不限于下述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-65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。In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more compounds of the above-mentioned ET-1 to ET-65, or adopt, but not limited to, one or more compounds of the following PH-1 to PH-46; Mixtures of one or more compounds of ET-1 to ET-65 and one or more of PH-1 to PH-46 may also be employed, but are not limited to.
Figure PCTCN2021114065-appb-000028
Figure PCTCN2021114065-appb-000028
Figure PCTCN2021114065-appb-000029
Figure PCTCN2021114065-appb-000029
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罗列的一种或多种的组合。The device may also include an electron injection layer between the electron transport layer and the cathode, and the material of the electron injection layer includes, but is not limited to, a combination of one or more of the following.
LiQ、LiF、NaCl、CsF、Li 2O、Cs 2CO 3、BaO、Na、Li、Ca、Mg、Yb。 LiQ, LiF, NaCl , CsF, Li2O , Cs2CO3 , BaO, Na, Li, Ca, Mg, Yb.
本发明的目的之四在于提供一种显示屏或显示面板，所述显示屏或显示面板中采用如目的之三所述的有机电致发光器件；作为优选，所述显示屏或显示面板为OLED显示器。The fourth object of the present invention is to provide a display screen or display panel, in which the organic electroluminescent device as described in the third object is used; preferably, the display screen or display panel is an OLED monitor.
本发明的目的之五在于提供一种电子设备，其中所述电子设备具有目的之四所述的显示屏或显示面板。The fifth object of the present invention is to provide an electronic device, wherein the electronic device has the display screen or display panel described in the fourth object.
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明在含硼化合物中引入一类含有螺烷烃结构的基团，这类螺烷烃结构可以有效的起到位阻作用，提升效率；另外这类螺烷烃结构，可以有效的改善分子跃迁偶极排列，实现更好的光取出效果，这几点共同作用，实现器件效率提升的技术优势。(1) In the present invention, a group containing a spiroalkane structure is introduced into the boron-containing compound, and this type of spiroalkane structure can effectively play a steric hindrance role and improve efficiency; in addition, this type of spiroalkane structure can effectively improve molecular transitions Dipole arrangement to achieve better light extraction effect, these points work together to achieve the technical advantage of improving device efficiency.
(2)本发明化合物的制备工艺简单易行，原料易得，适合于量产放大。(2) The preparation process of the compound of the present invention is simple and feasible, the raw materials are readily available, and it is suitable for mass production and scale-up.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.
本发明提供的新型含硼化合物的代表合成路径如下：The representative synthetic route of the novel boron-containing compound provided by the present invention is as follows:
方法一：method one:
Figure PCTCN2021114065-appb-000030
Figure PCTCN2021114065-appb-000030
方法二：Method Two:
Figure PCTCN2021114065-appb-000031
Figure PCTCN2021114065-appb-000031
方法三：Method three:
Figure PCTCN2021114065-appb-000032
Figure PCTCN2021114065-appb-000032
Figure PCTCN2021114065-appb-000033
Figure PCTCN2021114065-appb-000033
上述符号均具有与式(1)和式(H)中相同的意义。The above symbols all have the same meanings as in the formula (1) and the formula (H).
需要说明的是，获取本发明的化合物并不限于本发明中所用到的合成方法和原料，本领域技术人员也可以选取其它方法或路线得到本发明所提出的化合物。本发明中未提到的合成方法的化合物的都是通过商业途径获得的原料产品，或者通过这些原料产品依据公知的方法来进行自制。It should be noted that obtaining the compounds of the present invention is not limited to the synthetic methods and raw materials used in the present invention, and those skilled in the art can also select other methods or routes to obtain the compounds proposed by the present invention. The compounds of the synthetic methods not mentioned in the present invention are all raw materials obtained through commercial channels, or are self-made according to known methods through these raw materials.
以下合成例示例性地给出具体化合物的合成方法，其中中间体和化合物的分析检测使用ABSCIEX质谱仪(4000QTRAP)。The following synthesis examples exemplify the synthesis methods of specific compounds, wherein the analytical detection of intermediates and compounds uses an ABSCIEX mass spectrometer (4000QTRAP).
合成例1：M-17的合成Synthesis Example 1: Synthesis of M-17
Figure PCTCN2021114065-appb-000034
Figure PCTCN2021114065-appb-000034
中间体M17-1的制备：Preparation of Intermediate M17-1:
室温下向1L单口瓶中加4-(4-胺基苯基)环己酮(50g，264.19mmol，1eq)，无水乙醚(500mL)置换氮气三次，冰浴下向体系中滴加烯庚基氯化镁(158.5mL，317.03mmol，2mol/L的环己烷溶液，1.2eq)，室温反应2h。过滤，滤液浓缩除掉溶剂。Add 4-(4-aminophenyl)cyclohexanone (50g, 264.19mmol, 1eq) to a 1L single-necked flask at room temperature, replace nitrogen three times with anhydrous ether (500mL), and add eneheptyl dropwise to the system under ice bath magnesium chloride (158.5 mL, 317.03 mmol, 2 mol/L cyclohexane solution, 1.2 eq), and reacted at room temperature for 2 h. After filtration, the filtrate was concentrated to remove the solvent.
冰浴下，向剩余物中加入磷酸(200mL)，水(100mL)回流5h，冰浴下加入氢氧化钠水溶液中和至弱碱性，乙酸乙酯(500mL)萃取，浓缩，柱层析得到60g淡黄色油状物。Under ice bath, phosphoric acid (200 mL) was added to the residue, water (100 mL) was refluxed for 5 h, sodium hydroxide aqueous solution was added under ice bath to neutralize to weakly alkaline, extracted with ethyl acetate (500 mL), concentrated, and obtained by column chromatography 60g pale yellow oil.
中间体M17-2的合成：Synthesis of Intermediate M17-2:
将中间体M17-1(24.3g，100mmol，1eq)溶于300mL DMF中，在-40℃条件下缓慢加入含有NBS(35.5g，200mmol，2eq)的DMF溶液(100mL)，滴加完毕后，低温反应0.5h后。将反应体系加入水中，使用二氯甲烷(300mL)萃取，先使用亚硫酸钠溶液洗涤，后水洗数次后分液，减压蒸干，得白色固体28.9g。Intermediate M17-1 (24.3 g, 100 mmol, 1 eq) was dissolved in 300 mL of DMF, and a DMF solution (100 mL) containing NBS (35.5 g, 200 mmol, 2 eq) was slowly added at -40 °C. After the dropwise addition, After low temperature reaction for 0.5h. The reaction system was added to water, extracted with dichloromethane (300 mL), washed with sodium sulfite solution, washed with water several times, separated, evaporated to dryness under reduced pressure to obtain 28.9 g of a white solid.
中间体M17-3的合成：Synthesis of Intermediate M17-3:
向一个1L的单口烧瓶中加入特丁基亚硝酸酯(20.12g，195.07mmol，3eq)，氯化亚铜(19.31g，195.07mmol，3eq)，100mL乙腈溶解后，50℃氮气保护加热反应1h。后将中间体M17-2(26.06g，65mmol，1eq)溶于200mL乙腈中，缓慢滴加到反应体系中，50℃反应2h后停止反应，过滤蒸干，硅胶拌样使用纯石油醚柱层析。 得到白色固体13.5g。To a 1L single-necked flask was added tert-butyl nitrite (20.12g, 195.07mmol, 3eq), cuprous chloride (19.31g, 195.07mmol, 3eq), 100mL of acetonitrile was dissolved, heated at 50°C for 1h under nitrogen protection . After that, the intermediate M17-2 (26.06g, 65mmol, 1eq) was dissolved in 200mL of acetonitrile, slowly added dropwise to the reaction system, the reaction was stopped after 50 ℃ of reaction for 2h, filtered and evaporated to dryness, and the silica gel sample was mixed with pure petroleum ether column layer. analysis. 13.5 g of white solids were obtained.
中间体M17-4的合成：Synthesis of Intermediate M17-4:
室温下，将M17-3(8.4g，20mmol)，3,6-二叔丁基苯胺(16g，64mmol)，三(二亚苄基丙酮)二钯(Pd 2(dba) 3，0.56g，0.6mmol)，2-双环己基磷-2',6'-二甲氧基联苯(s-Phos，0.24g，0.6mmol)，叔丁醇钠(6.7g，70mmol)，二甲苯(300mL)加入至1L单口瓶中，氮气置换三次，加热至130℃反应过夜。反应液降至室温，以乙酸乙酯萃取，大量水洗，有机相干燥后浓缩进行柱层析，得到10.1g白色固体。 At room temperature, M17-3 (8.4 g, 20 mmol), 3,6-di-tert-butylaniline (16 g, 64 mmol), tris(dibenzylideneacetone)dipalladium (Pd 2 (dba) 3 , 0.56 g, 0.6 mmol), 2-dicyclohexylphosphorus-2',6'-dimethoxybiphenyl (s-Phos, 0.24 g, 0.6 mmol), sodium tert-butoxide (6.7 g, 70 mmol), xylene (300 mL) Put it into a 1L single-neck bottle, replace it with nitrogen three times, and heat it to 130° C. to react overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed with a large amount of water, the organic phase was dried, concentrated and subjected to column chromatography to obtain 10.1 g of white solid.
化合物M-17的合成：Synthesis of compound M-17:
将M17-4(8.2g，10mmol)加入至500mL三口瓶中，加入对叔丁基苯(t-BuPh，150mL)，搅拌20分钟后将反应体系降温至0℃，之后加入15mmol叔丁基锂(t-BuLi)，维持低温继续搅拌30分钟。之后逐步升温至60℃，持续加热3h。最后将反应体系温度再次降至-20℃，氮气保护下加入三溴化硼(5.1g，20mmol)，搅拌30分钟后加入二异丙基乙基胺(NEt(i-Pr) 2，13g，80mmol)。最后将反应体系加热至110℃，反应12h。反应降至室温后，将有机相减压旋干。乙酸乙酯(200mL)萃取三次，合并有机相，无水硫酸钠干燥。有机相拌硅胶浓缩，柱层析得2.7g粗品，甲苯/正己烷重结晶得1.65g黄色固体，纯度99.45％。质谱分析确定的分子离子质量：795.22(理论值：795.01)。 M17-4 (8.2g, 10mmol) was added into a 500mL there-necked flask, p-tert-butylbenzene (t-BuPh, 150mL) was added, the reaction system was cooled to 0°C after stirring for 20 minutes, and then 15mmol of tert-butyllithium was added. (t-BuLi), maintaining the low temperature and continuing to stir for 30 minutes. After that, the temperature was gradually increased to 60 °C, and the heating was continued for 3 h. Finally, the temperature of the reaction system was lowered to -20°C again, boron tribromide (5.1 g, 20 mmol) was added under nitrogen protection, and after stirring for 30 minutes, diisopropylethylamine (NEt(i-Pr) 2 , 13 g, 80 mmol). Finally, the reaction system was heated to 110 °C for 12 h. After the reaction had cooled to room temperature, the organic phase was spin-dried under reduced pressure. Ethyl acetate (200 mL) was extracted three times, and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, and 2.7 g of crude product was obtained by column chromatography, which was recrystallized from toluene/n-hexane to obtain 1.65 g of a yellow solid with a purity of 99.45%. Molecular ion mass determined by mass spectrometry: 795.22 (theoretical value: 795.01).
合成实施例2：M-69的合成Synthesis Example 2: Synthesis of M-69
Figure PCTCN2021114065-appb-000035
Figure PCTCN2021114065-appb-000035
中间体M69-1的制备：Preparation of Intermediate M69-1:
合成方案同M17-3的合成，将65mmol的M17-2替换为M17-1，柱层析后得到12.7g白色固体。The synthesis scheme was the same as the synthesis of M17-3, 65 mmol of M17-2 was replaced by M17-1, and 12.7 g of white solid was obtained after column chromatography.
中间体M69-2的合成：Synthesis of Intermediate M69-2:
室温下，将M69-1(10.4g，40mmol)，M17-1(13.8g，60mmol)，Pd 2(dba) 3(0.56g，0.6mmol)，s-P hos(0.24g，0.6mmol)，叔丁醇钠(NaOBut，6.7g，70mmol)，二甲苯(300mL)加入至1L单口瓶中，氮气置换三次，加热至130℃反应过夜。反应液降至室温，以乙酸乙酯萃取，大量水洗，有机相干燥后浓缩进行柱层析，得到13.7g白色固体。 At room temperature, M69-1 (10.4 g, 40 mmol), M17-1 (13.8 g, 60 mmol), Pd 2 (dba) 3 (0.56 g, 0.6 mmol), sP hos (0.24 g, 0.6 mmol), tert-butyl Sodium alkoxide (NaOBut, 6.7 g, 70 mmol) and xylene (300 mL) were added to a 1 L single-neck flask, replaced with nitrogen three times, and heated to 130° C. to react overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed with a large amount of water, and the organic phase was dried, concentrated, and subjected to column chromatography to obtain 13.7 g of white solid.
中间体M69-3的合成：Synthesis of Intermediate M69-3:
室温下，将M69-2(10.4g，40mmol)，1,3-二溴-2-氯-5-甲基苯(14g，50mmol)，Pd 2(dba) 3(0.56g，0.6mmol)，s-P hos(0.24g，0.6mmol)，叔丁醇钠(6.7g，70mmol)，二甲苯(300mL)加入至1L单口瓶中，氮气置换三次，加热至130℃反应过夜。反应液降至室温，以乙酸乙酯萃取，大量水洗，有机相干燥后浓缩进行柱层析，得到17.7g白色固体。 At room temperature, M69-2 (10.4 g, 40 mmol), 1,3-dibromo-2-chloro-5-methylbenzene (14 g, 50 mmol), Pd 2 (dba) 3 (0.56 g, 0.6 mmol), sP hos (0.24 g, 0.6 mmol), sodium tert-butoxide (6.7 g, 70 mmol), and xylene (300 mL) were added to a 1 L single-neck flask, replaced with nitrogen three times, and heated to 130° C. to react overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed with a large amount of water, the organic phase was dried, concentrated and subjected to column chromatography to obtain 17.7 g of white solid.
中间体M69-4的合成：Synthesis of Intermediate M69-4:
室温下，将M69-3(13.4g，20mmol)，二苯基胺(6.8g，40mmol)，Pd 2(dba) 3(0.28g，0.3mmol)，s-P hos(0.12g，0.3mmol)，叔丁醇钠(3.4g，35mmol)，二甲苯(200mL)加入至500mL单口瓶中，氮气置换三次，加热至130℃反应过夜。反应液降至室温，以乙酸乙酯萃取，大量水洗，有机相干燥后浓缩进行柱层析，得到10.7g白色固体。 At room temperature, M69-3 (13.4 g, 20 mmol), diphenylamine (6.8 g, 40 mmol), Pd 2 (dba) 3 (0.28 g, 0.3 mmol), sP hos (0.12 g, 0.3 mmol), tert. Sodium butoxide (3.4 g, 35 mmol) and xylene (200 mL) were added to a 500 mL single-neck flask, replaced with nitrogen three times, and heated to 130° C. to react overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed with a large amount of water, and the organic phase was dried, concentrated, and subjected to column chromatography to obtain 10.7 g of white solid.
化合物M-69的合成：Synthesis of compound M-69:
合成方案同M-17的合成，将M17-4替换为M69-4(10mmol)，提纯得1.46g黄色固体，纯度99.78％。质谱分析确定的分子离子质量：734.56(理论值：734.87)。The synthesis scheme was the same as the synthesis of M-17, M17-4 was replaced by M69-4 (10 mmol), and purified to obtain 1.46 g of a yellow solid with a purity of 99.78%. Molecular ion mass determined by mass spectrometry: 734.56 (theoretical value: 734.87).
其他化合物合成方法类似，根据相关合成通式进行合成，并进行了质谱测试确认，结果如下表所示：The synthesis methods of other compounds are similar, and they are synthesized according to the relevant synthetic formulas and confirmed by mass spectrometry tests. The results are shown in the following table:
化合物编号Compound number 质谱理论值Theoretical value of mass spectrometry 质谱测试数据Mass Spectrometry Test Data
M-1M-1 570.32570.32 570.47570.47
M-13M-13 570.32570.32 570.39570.39
M-24M-24 710.47710.47 710.56710.56
M-41M-41 622.35622.35 622.57622.57
M-50M-50 772.49772.49 772.83772.83
M-57M-57 874.44874.44 874.74874.74
M-66M-66 734.47734.47 734.58734.58
M-85M-85 838.53838.53 838.67838.67
M-89M-89 674.38674.38 674.49674.49
M-2M-2 556.30556.30 556.44556.44
M-6M-6 542.28542.28 542.67542.67
M-8M-8 542.28542.28 542.39542.39
M-7M-7 514.25514.25 514.45514.45
M-9M-9 528.27528.27 528.32528.32
M-11M-11 598.35598.35 598.45598.45
M-101M-101 528.39528.39 528.55528.55
M-102M-102 593.36593.36 593.73593.73
M-103M-103 508.24508.24 508.76508.76
M-104M-104 627.37627.37 627.53627.53
器件实施例1Device Example 1
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：乙醇混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreasing in an acetone:ethanol mixed solvent, baked in a clean environment until the water was completely removed, and UV light was used. Light and ozone cleaning, and bombarding the surface with a beam of low-energy cations;
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，5nm的化合物HT-14作为电子阻挡层；20nm的化合物BFH-4:M-1(100:3，w/w)二元混合物作为发光层，“100:3，w/w”指的是两种物质的重量比为100:3；5nm的ET-23作为空穴阻挡层，25nm的化合物 ET-61: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/秒，金属电极的蒸镀速率控制在1nm/秒。 The above-mentioned glass substrate with anode is placed in a vacuum chamber, evacuated to <1 × 10 -5 Pa, and 10nm of HT-4:HI-3 (97 nm) is vacuum thermally evaporated on the above-mentioned anode layer film in sequence. /3,w/w) mixture as hole injection layer, 60nm compound HT-4 as hole transport layer, 5nm compound HT-14 as electron blocking layer; 20nm compound BFH-4:M-1(100: 3, w/w) binary mixture as light-emitting layer, "100:3, w/w" means the weight ratio of the two substances is 100:3; 5nm ET-23 as hole blocking layer, 25nm compound The ET-61:ET-57 (50/50, w/w) mixture was used as the electron transport layer, 1 nm of LiF was used as the electron injection layer, and 150 nm of metallic aluminum was used as the cathode. The total evaporation rate of all organic layers and LiF was controlled at 0.1 nm/sec, and the evaporation rate of metal electrodes was controlled at 1 nm/sec.
器件实施例2～器件实施例21采用和器件实施例1同样的方法制作，区别仅在于将发光层的染料M-1分别进行替换，其他参数不变，具体见表1。Device Example 2 to Device Example 21 were fabricated by the same method as Device Example 1, except that the dye M-1 in the light-emitting layer was replaced respectively, and other parameters remained unchanged, see Table 1 for details.
器件比较例1～器件比较例2采用和器件实施例1同样的方法制作，区别仅在于将发光层里染料M-1分别替换成ref-1和ref-2(化合物获取方法参照CN110662750A)。Device Comparative Example 1 to Device Comparative Example 2 were fabricated by the same method as Device Example 1, except that the dye M-1 in the light-emitting layer was replaced by ref-1 and ref-2 respectively (refer to CN110662750A for the compound acquisition method).
Figure PCTCN2021114065-appb-000036
Figure PCTCN2021114065-appb-000036
器件性能测试：Device performance test:
对由上述过程制备的有机电致发光器件进行如下性能测定：The following performance measurements were performed on the organic electroluminescent devices prepared by the above process:
在同样亮度下，使用数字源表及PR650测定上述器件实施例和器件比较例中制备得到的有机电致发光器件的驱动电压和外量子效率。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1000cd/m 2时的电压即为对应亮度下的驱动电压，同时在PR650上可以直接测试得到器件的外量子效率(EQE％)； Under the same brightness, the driving voltage and external quantum efficiency of the organic electroluminescent devices prepared in the above device examples and device comparative examples were measured using a digital source meter and PR650. Specifically, the voltage is increased at a rate of 0.1V per second , and the voltage when the brightness of the organic electroluminescent device reaches 1000cd/m2 is determined as the driving voltage at the corresponding brightness. At the same time, the device can be directly tested on PR650. External quantum efficiency (EQE%);
有机电致发光器件性能如表1所示。The properties of the organic electroluminescent devices are shown in Table 1.
表1Table 1
Figure PCTCN2021114065-appb-000037
Figure PCTCN2021114065-appb-000037
Figure PCTCN2021114065-appb-000038
Figure PCTCN2021114065-appb-000038
以上结果表明，本发明的新型有机材料用于有机电致发光器件，实施例器件1-21相比于对比例器件1-2可以有效的降低工作电压，提高外量子效率，是性能良好的蓝光材料。The above results show that the novel organic material of the present invention is used in organic electroluminescence devices. Compared with the comparative example device 1-2, the example device 1-21 can effectively reduce the operating voltage and improve the external quantum efficiency, and is a blue light with good performance. Material.
本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明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，均落在本发明的保护范围和公开范围之内。The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (15)

  1. 一种化合物，所述化合物由式(1)所示的母核以及至少一个式(H)所示的取代基组成，且式(H)所示的取代基取代在式(1)所示的母核的任意可取代位置；A compound, the compound is composed of a parent nucleus represented by formula (1) and at least one substituent represented by formula (H), and the substituent represented by formula (H) is substituted in formula (1) any substitutable position of the parent nucleus;
    Figure PCTCN2021114065-appb-100001
    Figure PCTCN2021114065-appb-100001
    其中，*代表基团的连接键；Wherein, * represents the connecting bond of the group;
    式(1)中，所述环D、环G和环F独立地选自取代或未取代的C5～C60芳环或者取代或未取代的C3～C60杂芳环中的一种，所述取代的基团与相连接的芳环或杂芳环连接成环或不连接成环；In formula (1), the ring D, ring G and ring F are independently selected from a substituted or unsubstituted C5-C60 aromatic ring or a substituted or unsubstituted C3-C60 heteroaromatic ring, the substituted or unsubstituted C3-C60 heteroaromatic ring. The group is connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring;
    式(1)中，所述X 1和X 2独立地选自CR 1R 2、NR 3、O、S或SiR 4R 5中的一种，所述R 1、R 2、R 3、R 4和R 5独立地与相邻的环D、环G或环F连接成环或不连接成环； In formula (1), the X 1 and X 2 are independently selected from one of CR 1 R 2 , NR 3 , O, S or SiR 4 R 5 , the R 1 , R 2 , R 3 , R 5 4 and R 5 are independently connected to the adjacent Ring D, Ring G or Ring F to form a ring or not to form a ring;
    所述R 1、R 2、R 3、R 4和R 5独立地选自取代或未取代的C1～C20链状烷基、取代或未取代的C3～C20环烷基、取代或未取代的C6～C60芳基、取代或未取代的C3～C60杂芳基中的一种，所述取代的基团与相连接的芳环或杂芳环连接成环或不连接成环； The R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 cycloalkyl One of C6-C60 aryl group, substituted or unsubstituted C3-C60 heteroaryl group, the substituted group is connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring;
    式(H)中，所述环A和环E独立地选自取代或未取代的C3～C8脂肪环，所述取代的基团与相连接的脂肪环连接成环或不连接成环；In formula (H), the ring A and ring E are independently selected from substituted or unsubstituted C3-C8 aliphatic rings, and the substituted group is connected to the connected aliphatic ring to form a ring or not to form a ring;
    式(H)中，所述环A和环E通过共用一个sp3杂化的C原子进行连接；In formula (H), the ring A and the ring E are connected by sharing a sp3 hybridized C atom;
    环D、环G、环F、R 1、R 2、R 3、R 4、R 5、环A和环E中，所述取代的基团独立地选自卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种或者至少两种的组合。 In Ring D, Ring G, Ring F, R 1 , R 2 , R 3 , R 4 , R 5 , Ring A and Ring E, the substituted groups are independently selected from halogen, cyano, carbonyl, nitro , hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6- One or a combination of at least two C60 aryl groups and C3-C60 heteroaryl groups.
  2. 根据权利要求1所述的化合物，所述化合物由式(1)所示的母核以及一个或两个式(H)所示的取代基组成，且式(H)所示的取代基取代在式(1)所示的母核的任意可取代位置。The compound according to claim 1, which is composed of a parent nucleus represented by formula (1) and one or two substituents represented by formula (H), and the substituent represented by formula (H) is substituted in Any substitutable position of the parent nucleus represented by the formula (1).
  3. 根据权利要求1所述的化合物，所述X 1和X 2独立地选自NR 3、O或S中的一种，进一步优选NR 3。 The compound according to claim 1, wherein X 1 and X 2 are independently selected from one of NR 3 , O or S, more preferably NR 3 .
  4. 根据权利要求1所述的化合物，所述式(1)所示的母核具体为式(1-1)所示的结构；The compound according to claim 1, wherein the parent nucleus represented by the formula (1) is specifically the structure represented by the formula (1-1);
    Figure PCTCN2021114065-appb-100002
    Figure PCTCN2021114065-appb-100002
    式(1-1)中，所述环D、环G、环F和R 3均具有与权利要求1相同的限定范围； In formula (1-1), the ring D, ring G, ring F and R 3 all have the same limited scope as claim 1;
    所述R 3'具有与R 3相同的限定范围。 The R 3 ′ has the same defined range as R 3 .
  5. 根据权利要求1-4中任一项所述的化合物，所述环D、环G和环F独立地选自取代或未取代的C5～C30芳环或者取代或未取代的C3～C30杂芳环中的一种，优选取代或未取代的C5～C14芳环、取代或未取代的C3～C14杂芳环中的一种，进一步优选取代或未取代的C5～C8芳环或者取代或未取代的C5～C8杂芳环中的一种；The compound according to any one of claims 1-4, wherein the ring D, ring G and ring F are independently selected from substituted or unsubstituted C5-C30 aromatic rings or substituted or unsubstituted C3-C30 heteroaromatic rings One of the rings, preferably a substituted or unsubstituted C5-C14 aromatic ring, a substituted or unsubstituted C3-C14 heteroaromatic ring, more preferably a substituted or unsubstituted C5-C8 aromatic ring or a substituted or unsubstituted C5-C8 aromatic ring One of the substituted C5～C8 heteroaromatic rings;
    优选地，所述环D、环G和环F独立地选自式(b)所示的基团；Preferably, the ring D, ring G and ring F are independently selected from groups represented by formula (b);
    Figure PCTCN2021114065-appb-100003
    Figure PCTCN2021114065-appb-100003
    所述环D通过共享化学键c和化学键d与母核的其他部分连接；The ring D is connected to the rest of the parent core by sharing bonds c and d;
    所述环G和环F独立地通过共享化学键c或化学键d与母核的其他部分连接；Said Ring G and Ring F are independently connected to other parts of the parent core through shared bond c or bond d;
    式(b)中，所述Z 1、Z 2、Z 3和Z 4独立地选自CR 6或N，所述R 6独立地选自氢、卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R 6独立地与相连接的芳环或杂芳环连接成环或不连接成环。 In formula (b), the Z 1 , Z 2 , Z 3 and Z 4 are independently selected from CR 6 or N, and the R 6 is independently selected from hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, Amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl , one of C3-C60 heteroaryl groups, the R 6 is independently connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring.
  6. 根据权利要求1所述的化合物，所述式(1)所示的母核具体为式(1-1-1)、式(1-1-2)或式(1-1-3)所示的结构，优选式(1-1-1)所示的结构；The compound according to claim 1, wherein the parent nucleus represented by the formula (1) is specifically represented by the formula (1-1-1), the formula (1-1-2) or the formula (1-1-3) The structure, preferably the structure shown in formula (1-1-1);
    Figure PCTCN2021114065-appb-100004
    Figure PCTCN2021114065-appb-100004
    Figure PCTCN2021114065-appb-100005
    Figure PCTCN2021114065-appb-100005
    所述Z 1、Z 1'、Z 1”、Z 2、Z 2'、Z 2”、Z 3、Z 3'、Z 3”、Z 4和Z 4'独立地选自CR 6或N，所述R 6独立地选自氢、卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R 6独立地与相连接的芳环或杂芳环连接成环或不连接成环； The Z 1 , Z 1 ′, Z 1 ″, Z 2 , Z 2 ′, Z 2 ″, Z 3 , Z 3 ′, Z 3 ″, Z 4 and Z 4 ′ are independently selected from CR 6 or N, The R 6 is independently selected from hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silane one of C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C60 aryl group, C3-C60 heteroaryl group, the R 6 is independently connected to the connected aromatic ring or heteroaromatic ring Connected into a ring or not connected into a ring;
    所述Z 5、Z 5'、Z 6、Z 6'、Z 7、Z 7'、Z 8和Z 8'独立地选自CR 7或N，所述R 7独立地选自氢、卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R 7独立地与相连接的芳环或杂芳环连接成环或不连接成环； Said Z 5 , Z 5 ', Z 6 , Z 6 ', Z 7 , Z 7 ', Z 8 and Z 8 ' are independently selected from CR 7 or N, and said R 7 is independently selected from hydrogen, halogen, Cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 One of heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl, the R 7 is independently connected to the connected aromatic ring or heteroaromatic ring to form a ring or not to form a ring;
    所述R 3具有与权利要求1相同的限定范围，所述R 3'具有与R 3相同的限定范围； The R 3 has the same limited scope as claim 1, and the R 3 ' has the same limited scope as R 3 ;
    优选地，所述Z 5、Z 6、Z 7和Z 8中至多有两个为N，和/或，所述Z 5'、Z 6'、Z 7'和Z 8'中至多有两个为N。 Preferably, at most two of said Z 5 , Z 6 , Z 7 and Z 8 are N, and/or at most two of said Z 5 ', Z 6 ', Z 7 ' and Z 8 ' is N.
  7. 根据权利要求1-6中任一项所述的化合物，所述R 3选自取代或未取代的C6～C60芳基、取代或未取代的C3～C60杂芳基中的一种；优选取代或未取代的C6～C30芳基；进一步优选取代或未取代的苯基； The compound according to any one of claims 1-6, wherein the R 3 is selected from one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; preferably substituted or unsubstituted C6-C30 aryl; further preferably substituted or unsubstituted phenyl;
    优选地，R 3中，所述取代的基团选自C1～C20链状烷基或C6～C60芳基中的任意一种或至少两种组合，优选甲基、异丙基、叔丁基、苯基中的任意一种或至少两种组合。 Preferably, in R 3 , the substituted group is selected from any one of C1-C20 chain alkyl or C6-C60 aryl, or a combination of at least two, preferably methyl, isopropyl, tert-butyl , any one of phenyl groups or a combination of at least two of them.
  8. 根据权利要求1-7中任一项所述的化合物，所述式(H)所示的取代基具体为式(H')所示的结构；The compound according to any one of claims 1-7, wherein the substituent represented by the formula (H) is specifically the structure represented by the formula (H');
    Figure PCTCN2021114065-appb-100006
    Figure PCTCN2021114065-appb-100006
    式(H')中，*代表基团的连接键；In formula (H'), * represents the connecting bond of the group;
    式(H')中，所述m和n独立地为0～5的整数，r和s各自独立地为0～6的整数；In formula (H'), the m and n are independently an integer from 0 to 5, and r and s are each independently an integer from 0 to 6;
    式(H')中，所述R a和R b独立地选自卤素、氰基、羰基、硝基、羟基、氨基、C1～C20链状烷基、C3～C20环烷基、C1～C20烷氧基、C1～C20硅烷基、C6～C60芳基氨基、C3～C60杂芳基氨基、C6～C60芳基、C3～C60杂芳基中的一种，所述R a和R b独立地与相连接的脂肪环连接成环或不连接成环。 In formula (H'), R a and R b are independently selected from halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 A kind of alkoxy group, C1-C20 silyl group, C6-C60 arylamino group, C3-C60 heteroarylamino group, C6-C60 aryl group, C3-C60 heteroaryl group, the R a and R b are independent The ground is connected to the connected aliphatic ring to form a ring or not to form a ring.
  9. 根据权利要求8所述的化合物，所述式(H')所示的取代基具体为式(H-1)至式(H-6) 所示的结构中的一种，优选式(H-1)所示的结构；The compound according to claim 8, the substituent represented by the formula (H') is specifically one of the structures represented by the formula (H-1) to the formula (H-6), preferably the formula (H- 1) The structure shown;
    Figure PCTCN2021114065-appb-100007
    Figure PCTCN2021114065-appb-100007
    其中，*代表基团的连接键；Wherein, * represents the connecting bond of the group;
    所述R a、R b、r和s均具有与权利要求8相同的限定范围。 Said R a , R b , r and s all have the same defined range as claim 8 .
  10. 根据权利要求8或9所述的化合物，所述R a和R b独立地选自C1～C20链状烷基，优选甲基或正丁基； The compound according to claim 8 or 9, wherein R a and R b are independently selected from C1-C20 chain alkyl, preferably methyl or n-butyl;
    优选地，所述r和s的独立地为0～2，优选为0。Preferably, the r and s are independently 0 to 2, preferably 0.
  11. 根据权利要求1所述的化合物，所述式(H)所示的取代基具体选自如下基团中的一种：The compound according to claim 1, the substituent shown in the formula (H) is specifically selected from one of the following groups:
    Figure PCTCN2021114065-appb-100008
    Figure PCTCN2021114065-appb-100008
    其中，*代表基团的连接键。Wherein, * represents the connecting bond of the group.
  12. 根据权利要求1所述的化合物，所述化合物具有M1-M104所述的结构中的任意一种；The compound according to claim 1, which has any one of the structures described in M1-M104;
    Figure PCTCN2021114065-appb-100009
    Figure PCTCN2021114065-appb-100009
    Figure PCTCN2021114065-appb-100010
    Figure PCTCN2021114065-appb-100010
    Figure PCTCN2021114065-appb-100011
    Figure PCTCN2021114065-appb-100011
    Figure PCTCN2021114065-appb-100012
    Figure PCTCN2021114065-appb-100012
    Figure PCTCN2021114065-appb-100013
    Figure PCTCN2021114065-appb-100013
  13. 一种根据权利要求1-12中任一项所述的化合物的应用，所述化合物用于有机电致发光 器件；优选地，所述化合物在所述有机电致发光器件中作为发光层材料，优选发光染料。An application of the compound according to any one of claims 1-12, the compound is used in an organic electroluminescent device; preferably, the compound is used as a light-emitting layer material in the organic electroluminescent device, Luminescent dyes are preferred.
  14. 一种有机电致发光器件，所述有机电致发光器件包括基板，以及依次形成在所述基板上的第一电极、有机层和第二电极，所述有机层中含有权利要求1-12中任一项所述的化合物；优选地，所述有机层包括发光层，所述发光层中含有权利要求1-12中任一项所述的化合物。An organic electroluminescence device, the organic electroluminescence device comprises a substrate, and a first electrode, an organic layer and a second electrode sequentially formed on the substrate, wherein the organic layer contains one of claims 1-12 The compound of any one; preferably, the organic layer includes a light-emitting layer, and the light-emitting layer contains the compound of any one of claims 1-12.
  15. 根据权利要求14所述的有机电致发光器件，所述有机电致发光器件为蓝光器件，优选发光波长≤500nm，更优选≤475nm。The organic electroluminescent device according to claim 14, wherein the organic electroluminescent device is a blue light device, preferably the emission wavelength is ≤500 nm, more preferably ≤475 nm.
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