WO2021203673A1 - Nitrogen containing compound, organic electroluminescent device using same, and electronic device - Google Patents

Nitrogen containing compound, organic electroluminescent device using same, and electronic device Download PDF

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WO2021203673A1
WO2021203673A1 PCT/CN2020/122273 CN2020122273W WO2021203673A1 WO 2021203673 A1 WO2021203673 A1 WO 2021203673A1 CN 2020122273 W CN2020122273 W CN 2020122273W WO 2021203673 A1 WO2021203673 A1 WO 2021203673A1
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carbon atoms
group
groups
substituted
ring
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PCT/CN2020/122273
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French (fr)
Chinese (zh)
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郑奕奕
马天天
刘新颖
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陕西莱特光电材料股份有限公司
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Publication of WO2021203673A1 publication Critical patent/WO2021203673A1/en

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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
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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    • C09K2211/1018—Heterocyclic compounds
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    • H10K2101/10—Triplet emission

Definitions

  • the invention belongs to the technical field of organic electroluminescent materials, and specifically relates to a nitrogen-containing compound, an organic electroluminescent device and an electronic device using the nitrogen-containing compound.
  • An organic electroluminescent device such as an organic light emitting diode (OLED) usually includes a cathode and an anode disposed opposite to each other, and a functional layer disposed between the cathode and the anode.
  • the functional layer is composed of multiple organic or inorganic film layers, and generally includes an organic light-emitting layer, a hole transport layer between the organic light-emitting layer and the anode, and an electron transport layer between the organic light-emitting layer and the cathode. When voltage is applied to the cathode and anode, the two electrodes generate an electric field.
  • the electrons on the cathode side move to the electroluminescent layer
  • the holes on the anode side also move to the light emitting layer
  • the electrons and holes are combined in the electroluminescent layer.
  • Excitons are formed, and the excitons are in an excited state to release energy to the outside, so that the electroluminescent layer emits light to the outside.
  • CN104039778A, etc. disclose materials that can be used to prepare a light-emitting layer in an organic electroluminescent device.
  • current organic electroluminescent materials still have the problems of short luminous life and low luminous efficiency. Therefore, it is necessary to continue to develop new materials to further improve the life and efficiency performance of organic electroluminescent devices.
  • the purpose of the present invention is to provide an organic electroluminescent material with excellent performance, which can be used as a light-emitting layer in an organic electroluminescent device.
  • the present invention provides a nitrogen-containing compound, the structural formula of the nitrogen-containing compound is shown in the chemical formula (1):
  • ring A is a fused aromatic ring with 10 to 14 carbon atoms or a fused heteroaromatic ring with 8 to 12 carbon atoms, and the ring A is not a carbazole ring;
  • Ring B is a benzene ring, a fused aromatic ring with 10 to 14 carbon atoms, or a fused heteroaromatic ring with 8 to 12 carbon atoms;
  • Ring C is a benzene ring or a condensed aromatic ring with 10-14 carbon atoms
  • R 1 , R 2 , R 3 , and R 4 are the same or different from each other and are each independently selected from deuterium, halogen group, cyano group, halogenated alkyl group having 1 to 12 carbon atoms, and one having 1 to 12 carbon atoms Alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, heterocycloalkyl groups having 2 to 10 carbon atoms, Alkoxy groups having 1 to 12 carbon atoms, alkylthio groups having 1 to 12 carbon atoms, trialkylsilyl groups having 3 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, carbon A heteroaryl group having 3 to 20 atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and an arylsilyl group having 6 to 18 carbon atom
  • n 1 represents the number of substituents R 1
  • n 2 represents the number of substituents R 2
  • n 3 represents the number of substituents R 3
  • n 4 represents the number of substituents R 4
  • n 1 , n 2 , n 3 and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4;
  • n 1 is greater than 1, any two of R 1 are the same or different; when n 2 is greater than 1, any two of R 2 are the same or different; when n 3 is greater than 1, any two of R 3 Same or different, when n 4 is greater than 1, any two of the R 4 are the same or different;
  • W is selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms;
  • the substituents in W are the same or different, and are independently selected from the group consisting of deuterium, halogen group, cyano group, alkyl group with 1-12 carbon atoms, and 1-12 carbon atoms.
  • Aralkyl optionally substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl, aryl groups having 6 to 30 carbon atoms, optionally Heteroaryl groups having 3 to 30 carbon atoms and 1 to 12 carbon atoms substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl
  • the two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5 ⁇ 18-membered aliphatic ring or 5-18-membered aromatic ring.
  • an organic electroluminescent device includes an anode and a cathode disposed oppositely, and a functional layer disposed between the anode and the cathode; the function The layer contains the aforementioned nitrogen-containing compound.
  • an electronic device including the organic electroluminescent device of the present application.
  • the adamantane spiro-fused fluorenyl group as a part of the core of the nitrogen-containing compound has strong rigidity and the first triplet energy level, and the carbazole ring conjugated to the fused fluorenyl group in the compound has With better hole transport ability, the nitrogen-containing compound of the present application is suitable as the host material of the light-emitting layer in an organic electroluminescent device.
  • the adamantyl group and the fluorenyl group are spiro, which can greatly increase the electron cloud density of the large planar conjugated structure through the hyperconjugation effect, enhance the hole mobility of the nitrogen-containing compound, and help promote the exchange of holes and electrons in the light-emitting layer Transmission balance improves the efficiency performance of organic electroluminescent devices.
  • the improvement of the hole transport performance of nitrogen-containing compounds can increase the recombination rate of electrons and holes in the organic light-emitting layer, reduce or prevent electrons from passing through the organic light-emitting layer to the hole transport layer, thereby effectively protecting The hole transport layer material is protected from the impact of electrons, and the life of the organic electroluminescent device is improved.
  • the adamantyl group screwed on the fluorene group has a large space volume and strong rigidity, so it can reduce the interaction force between the large plane conjugated structure, reduce the intermolecular ⁇ - ⁇ stacking, and adjust The degree of intermolecular stacking in turn enables the nitrogen-containing compound to have a more stable amorphous state during film formation, improves the film-forming properties of the nitrogen-containing compound, and further increases the life of the organic electroluminescent device.
  • Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present application.
  • Fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
  • Electron injection layer 100.
  • the number of carbon atoms of W refers to the number of all carbon atoms. For example, if W is selected from substituted aryl groups with 40 carbon atoms, all carbon atoms of the aryl group and the substituents thereon are 40; if W is 9,9-dimethylfluorenyl, then It belongs to the substituted fluorenyl group with 15 carbon atoms, and the ring carbon atom number of W is 13.
  • the number of carbon atoms of a substituted aryl or heteroaryl group in L and Ar refers to the total number of carbon atoms of the aryl or heteroaryl group and its substituents, for example, the number of carbon atoms is 18.
  • the substituted aryl group means that the total number of carbon atoms of the aryl group and the substituent is 18.
  • 2,4-diphenyl-1,3,5-triazinyl is a substituted heteroaryl group with 15 carbon atoms.
  • substituted or unsubstituted aryl group having 6 to 40 carbon atoms and “substituted or unsubstituted aryl group having 6 to 40 carbon atoms” have the same meaning, and both refer to aryl groups.
  • the total number of carbon atoms of the substituents thereon is 6-40.
  • substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms and “substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms” have the same meaning. Both mean that the total number of carbon atoms of the heteroaryl group and the substituents thereon is 3-30.
  • substituted or unsubstituted aryl group having 6 to 40 carbon atoms and “substituted or unsubstituted aryl group having 6 to 40 carbon atoms” have the same meaning, and both refer to aryl groups.
  • the total number of carbon atoms of the substituents thereon is 6-40.
  • substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms and “substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms” have the same meaning. Both mean that the total number of carbon atoms of the heteroaryl group and the substituents thereon is 3-30.
  • hetero means that a functional group includes at least one heteroatom such as B, N, O, S, Se, Si, or P, and the remaining atoms are carbon and hydrogen.
  • the unsubstituted alkyl group may be a "saturated alkyl group" without any double or triple bonds.
  • each q is independently 0, 1, 2 or 3
  • each R independently selected from hydrogen, fluorine, and chlorine in the description
  • formula Q-1 represents that there are q substituents R on the benzene ring ", each R” can be the same or different, and the options of each R" do not affect each other
  • formula Q-2 means that there are q substituents R" on each benzene ring of biphenyl, and the two benzene rings
  • the number q of R" substituents may be the same or different, and each R" may be the same or different, and the options of each R" do not affect each other.
  • heterocyclic group optionally substituted by an alkyl group means that an alkyl group may but does not have to be present, and the description includes the scenario where the heterocyclic group is substituted by an alkyl group and the scenario where the heterocyclic group is not substituted by an alkyl group.
  • “Two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5- to 18-membered aliphatic ring or 5- to 18-membered aromatic ring with the atoms they are commonly connected to” means that they are connected to the same atom
  • the two substituents on the above can form a ring but do not have to form a ring, including the situation where the two are connected to form a saturated or unsaturated 5-18 membered aliphatic ring or a 5-18 membered aromatic ring, and also include the two independent of each other The scene of the existence of the earth.
  • substituted or unsubstituted means that it has no substituents or is substituted by one or more substituents.
  • the substituents include, but are not limited to, deuterium, halogen groups (F, Cl, Br), cyano, alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, aryloxy, arylsulfide Group, alkylamino group, cycloalkyl group, heterocyclic group, trialkylsilyl group, alkyl group, cycloalkyl group, alkoxy group, alkylthio group.
  • alkyl may include linear or branched alkyl.
  • Alkyl groups can have 1 to 12 carbon atoms.
  • a numerical range such as “1 to 12” refers to each integer in the given range; for example, "1 to 12 carbon atoms” means that it can contain 1 Carbon atoms, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 A carbon atom, 12 carbon atom alkyl group.
  • the alkyl group may also be a medium-sized alkyl group having 1 to 10 carbon atoms.
  • the alkyl group may also be a lower alkyl group having 1 to 6 carbon atoms. In still other embodiments, the alkyl group contains 1-4 carbon atoms; in still other embodiments, the alkyl group contains 1-3 carbon atoms.
  • the alkyl group may be optionally substituted with one or more substituents described in the present invention.
  • alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), isopropyl (i-Pr, -CH(CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH(CH 3 )CH 2 CH 3 ), tert-butyl (t-Bu, -C(CH 3 ) 3 ), etc.
  • the alkyl group may be substituted or unsubstituted.
  • alkenyl refers to a hydrocarbon group containing one or more double bonds in a straight or branched hydrocarbon chain. Alkenyl groups can be unsubstituted or substituted. Alkenyl groups can have 2 to 12 carbon atoms, and whenever it appears herein, a numerical range such as “2 to 12" refers to each integer in the given range; for example, “2 to 20 carbon atoms” means that Contains 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms , Alkenyl of 12 carbon atoms.
  • the alkenyl group may be vinyl, butadiene, or 1,3,5-hexatriene.
  • cycloalkyl refers to cyclic saturated hydrocarbons, including monocyclic and polycyclic structures.
  • Cycloalkyl groups can have 3 to 12 carbon atoms, and a numerical range such as “3 to 12" refers to each integer in the given range; for example, "3 to 12 carbon atoms” means that it can contain 3 carbon atoms, Cycloalkyl groups of 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, and 12 carbon atoms. Cycloalkyl groups can also be classified as monocyclic (only one ring), bicyclic (two rings), or polycyclic (three or more rings).
  • Cycloalkyl groups can also be divided into two rings sharing one carbon atom (spiro ring), two rings sharing two carbon atoms (fused ring), and two rings sharing two or more carbon atoms (bridged ring).
  • cycloalkyl groups may be substituted or unsubstituted.
  • the cycloalkyl group is a 5- to 10-membered cycloalkyl group.
  • the cycloalkyl group is a 5- to 8-membered cycloalkyl group.
  • examples of the cycloalkyl group may be, but are not limited to : Five-membered cycloalkyl is cyclopentyl, six-membered cycloalkyl is cyclohexyl, 10-membered polycyclic alkyl such as adamantyl, etc.
  • the halogen group as the substituent includes fluorine, chlorine, bromine or iodine.
  • alkoxy means that the alkyl group is connected to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described in the present invention. Unless otherwise specified, the alkoxy group contains 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in another embodiment, the alkoxy group The group contains 1 to 3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents described in this invention.
  • alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3 ), ethoxy (EtO, -OCH 2 CH 3 ), 1-propoxy (n-PrO, n- Propoxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH(CH 3 ) 2 ), 1-butoxy (n-BuO, n- Butoxy, -OCH 2 CH 2 CH 2 CH 3 ), 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH 2 CH(CH 3 ) 2 ), 2-but Oxygen (s-BuO, s-butoxy, -OCH(CH 3 )CH 2 CH 3 ), 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC(CH 3 ) 3 ), etc.
  • haloalkyl or “haloalkoxy” means that an alkyl group or an alkoxy group is substituted by one or more halogen atoms, wherein the alkyl group and the alkoxy group have the meaning as described in the present invention
  • alkyl group and the alkoxy group have the meaning as described in the present invention
  • examples include, but are not limited to, trifluoromethyl, trifluoromethoxy, and the like.
  • an aryl group refers to an optional functional group or substituent derived from an aromatic carbocyclic ring.
  • the aryl group can be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group can be a monocyclic aryl group, a condensed ring aryl group, two or more monocyclic aryl groups conjugated by a carbon-carbon bond, through A monocyclic aryl group and a fused ring aryl group conjugated by carbon-carbon bonds, and two or more fused ring aryl groups conjugated by a carbon-carbon bond. That is, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in the present application.
  • the aryl group does not contain heteroatoms such as B, N, O, S, P, and Si.
  • biphenyl, terphenyl, etc. are aryl groups.
  • aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, benzo[9,10] Phenanthryl, pyrenyl, benzofluoranthene, Base and so on.
  • the substituted aryl group may be one or more hydrogen atoms in the aryl group, such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, Cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, aryl, heterocyclic and other groups are substituted.
  • aryl group such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, Cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, aryl, heterocyclic and other groups are substituted.
  • heteroaryl-substituted aryl groups include, but are not limited to, dibenzofuranyl-substituted phenyl groups, dibenzothiophene-substituted phenyl groups, pyridine-substituted phenyl groups, and the like.
  • the number of carbon atoms of a substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group.
  • a substituted aryl group with 18 carbon atoms refers to an aryl group and its The total number of carbon atoms of the substituent is 18.
  • the fluorenyl group as an aryl group can be substituted, and two substituent groups can be combined with each other to form a spiro structure.
  • Specific examples include but are not limited to the following structures:
  • a heteroaryl group refers to a monovalent aromatic ring containing at least one heteroatom in the ring or a derivative thereof.
  • the heteroatom may be at least one of B, O, N, P, Si, and S.
  • the heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group.
  • the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated through carbon-carbon bonds, and any aromatic
  • the ring system is an aromatic monocyclic ring or an aromatic fused ring.
  • the "heteroaryl group” in this application may include 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 heteroatoms selected from B, O, N, P, Si, Se and S ,
  • the number of carbon atoms can be 3 to 40, in some embodiments, the number of carbon atoms of the heteroaryl group can be 3 to 30, in other embodiments, the number of carbon atoms of the heteroaryl group can be 3 to 20 , Or 3 to 18, or 3 to 12, or 12 to 18.
  • the number of carbon atoms of a heteroaryl group can also be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 18, 20 or 40.
  • the number of carbon atoms can also be other numbers, so I won't list them all here.
  • heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, Acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazine Azinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thiophene Thienyl, benzofur
  • thienyl, furanyl, phenanthrolinyl, etc. are heteroaryl groups of a single aromatic ring system type
  • N-arylcarbazolyl and N-heteroarylcarbazolyl are multiple groups conjugated through carbon-carbon bonds.
  • Heteroaryl group of ring system type is heteroaryl group of ring system type.
  • the substituted heteroaryl group may be one or more hydrogen atoms in the heteroaryl group, such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkane Group, cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, aryl, heterocyclic and other groups are substituted.
  • the heteroaryl group such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkane Group, cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, aryl, heterocyclic and other groups are substituted.
  • aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, phenyl-substituted pyridyl, and the like. It should be understood that the number of carbon atoms of the substituted heteroaryl group refers to the total number of carbon atoms of the heteroaryl group and the substituents on the heteroaryl group.
  • R G1 , R G2 , and R G3 are each independently an alkyl group.
  • Specific examples of the alkylsilyl group include, but are not limited to, trimethylsilyl group, triethylsilyl group, and tert-butyldimethylsilyl group. , Propyldimethylsilyl.
  • arylsilyl refers to Wherein, R G4 , R G5 , and R G6 are each independently an aryl group. Specific examples of the arylsilyl group include, but are not limited to, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc., but not Not limited to this.
  • a heteroaryl group with 3 to n ring carbon atoms means that the number of carbon atoms in the heteroaryl ring is 3 to n, and the carbon in the substituent on the heteroaryl group The number of atoms is not counted.
  • aryl can be applied to arylene
  • heteroaryl can be applied to heteroarylene
  • alkyl can be applied to alkylene
  • cycloalkyl can be Applied to cycloalkylene
  • the ring system formed by n atoms is an n-membered ring.
  • phenyl is a 6-membered aryl group.
  • 6-10 membered aromatic ring refers to benzene ring, indene ring, naphthalene ring and so on.
  • the "ring” in this application includes saturated rings and unsaturated rings; saturated rings are cycloalkyl, heterocycloalkyl, and unsaturated rings, namely cycloalkenyl, heterocycloalkenyl, aryl and heteroaryl.
  • the non-positioned link in this application refers to the single bond extending from the ring system or It means that one end of the link can be connected to any position in the ring system that the bond penetrates, and the other end is connected to the rest of the compound molecule.
  • the naphthyl group represented by the formula (X) is connected to other positions of the molecule through two non-positioned linkages running through the bicyclic ring. ) ⁇ Any possible connection shown in formula (X-10).
  • the phenanthryl group represented by the formula (X') is connected to other positions of the molecule through a non-positional linkage extending from the middle of the benzene ring on one side. It includes any possible connection modes shown in formula (X'-1) to formula (X'-4).
  • the non-positional substituent in this application refers to a substituent connected by a single bond extending from the center of the ring system, which means that the substituent can be attached to any possible position in the ring system.
  • the substituent R group represented by the formula (Y) is connected to the quinoline ring through a non-localized linkage, and its meaning includes the following formula (Y-1) to Any possible connection mode shown in formula (Y-7).
  • the present application provides a nitrogen-containing compound, the structural formula of the nitrogen-containing compound is shown in the chemical formula (1):
  • ring A is a fused aromatic ring with 10 to 14 carbon atoms or a fused heteroaromatic ring with 8 to 12 carbon atoms, and the ring A is not a carbazole ring;
  • Ring B is a benzene ring, a fused aromatic ring with 10 to 14 carbon atoms, or a fused heteroaromatic ring with 8 to 12 carbon atoms;
  • Ring C is a benzene ring or a condensed aromatic ring with 10-14 carbon atoms
  • R 1 , R 2 , R 3 , and R 4 are the same or different from each other and are each independently selected from deuterium, halogen group, cyano group, halogenated alkyl group having 1 to 12 carbon atoms, and one having 1 to 12 carbon atoms Alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, heterocycloalkyl groups having 2 to 10 carbon atoms, Alkoxy groups having 1 to 12 carbon atoms, alkylthio groups having 1 to 12 carbon atoms, trialkylsilyl groups having 3 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, carbon A heteroaryl group having 3 to 20 atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and an arylsilyl group having 6 to 18 carbon atom
  • n 1 represents the number of substituents R 1
  • n 2 represents the number of substituents R 2
  • n 3 represents the number of substituents R 3
  • n 4 represents the number of substituents R 4
  • n 1 , n 2 , n 3 and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4;
  • n 1 is greater than 1, any two of R 1 are the same or different; when n 2 is greater than 1, any two of R 2 are the same or different; when n 3 is greater than 1, any two of R 3 The same or different; when n 4 is greater than 1, any two of the R 4 are the same or different;
  • W is selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms;
  • the substituents in W are the same or different, and are independently selected from the group consisting of deuterium, halogen group, cyano group, alkyl group with 1-12 carbon atoms, and 1-12 carbon atoms.
  • Aralkyl optionally substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl, aryl groups having 6 to 30 carbon atoms, optionally Heteroaryl groups having 3 to 30 carbon atoms and 1 to 12 carbon atoms substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl
  • the two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5 ⁇ 18-membered aliphatic ring or 5-18-membered aromatic ring.
  • ring A refers to Ring B refers to Among them, ring A is independently a fused aromatic ring or a fused heteroaromatic ring; ring B is independently a benzene ring, a fused aromatic ring, or a fused heteroaromatic ring, such as naphthalene ring, anthracene ring, phenanthrene ring, quinoline Ring, isoquinoline ring, etc. in, Represents a chemical bond.
  • ring A is a naphthalene ring, and the number of substituents R 1 on ring A is 0;
  • ring B is a naphthalene ring, and the number of substituents R 2 on ring B is 0.
  • ring B includes at least one benzene ring structure, which makes the nitrogen-containing compound of the present application include at least one carbazole structure.
  • the adamantane spiro-fused fluorenyl group as a part of the core of the nitrogen-containing compound has strong rigidity and the first triplet energy level, and the carbazole ring conjugated to the fused fluorenyl group in the compound has With better hole transport ability, the nitrogen-containing compound of the present application is suitable as the host material of the light-emitting layer in an organic electroluminescent device.
  • the adamantyl group and the fluorenyl group are spiro, which can greatly increase the electron cloud density of the large planar conjugated structure through the hyperconjugation effect, enhance the hole mobility of the nitrogen-containing compound, and help promote the exchange of holes and electrons in the light-emitting layer Transmission balance improves the efficiency performance of organic electroluminescent devices.
  • the improvement of the hole transport performance of nitrogen-containing compounds can increase the recombination rate of electrons and holes in the organic light-emitting layer, reduce or prevent electrons from passing through the organic light-emitting layer to the hole transport layer, thereby effectively protecting The hole transport layer material is protected from the impact of electrons, and the life of the organic electroluminescent device is improved.
  • the adamantyl group screwed on the fluorene group has a large space volume and strong rigidity, so it can reduce the interaction force between the large plane conjugated structure, reduce the intermolecular ⁇ - ⁇ stacking, and adjust The degree of intermolecular stacking in turn enables the nitrogen-containing compound to have a more stable amorphous state during film formation, improves the film-forming properties of the nitrogen-containing compound, and further increases the life of the organic electroluminescent device.
  • the ring A in the formula (1) is a naphthalene ring, an anthracene ring, a phenanthrene ring, a dibenzofuran ring, a dibenzothiophene ring, a thianthene ring, a phenoxathi Ring, dibenzodioxin ring, 10H-phenothiazine or 10H-phenoxazine;
  • said ring B is benzene ring, naphthalene ring, quinoline ring or isoquinoline ring;
  • said ring C is selected from benzene ring , Naphthalene ring, anthracene ring or phenanthrene ring.
  • the ring A in the nitrogen-containing compound is a condensed aromatic ring structure
  • the large-planar conjugated structure of the nitrogen-containing compound is larger, more rigid, and has a higher electron cloud density, which makes the nitrogen-containing compound more capable of transporting holes
  • it can increase the recombination rate of electrons and holes in the organic light-emitting layer, reduce or prevent electrons from passing through the organic light-emitting layer to the hole transport layer, and can effectively protect the hole transport layer material from the impact of electrons. Improve the lifetime of the organic electroluminescence device to emit light.
  • the number of carbon atoms of R 1 , R 2 , R 3 , R 4 and W refers to the number of all carbon atoms.
  • W is selected from substituted aryl groups having 10 carbon atoms
  • all carbon atoms of the aryl group and the substituents thereon are 10.
  • W is a p-tert-butylphenyl group
  • W is a substituted phenyl group having 10 carbon atoms
  • W has 6 ring carbon atoms.
  • hetero means that a functional group includes at least one heteroatom such as B, N, O, S, Se, Si, or P, and the remaining atoms are carbon and hydrogen.
  • the unsubstituted alkyl group may be a "saturated alkyl group" without any double or triple bonds.
  • the number of carbon atoms of the substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group.
  • the substituted aryl group with 18 carbon atoms means that the total number of carbon atoms of the aryl group and the substituent on the aryl group is 18.
  • 9,9-dimethylfluorenyl is a substituted aryl group having 15 carbon atoms.
  • the structural formula of the nitrogen-containing compound of the present application is shown in any one of chemical formulas (f-1) to (f-16):
  • the structural formula of the nitrogen-containing compound is shown in any one of chemical formulas (f-17) to (f-32):
  • W is wherein, L is each independently selected from a single bond, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms;
  • Ar is selected from A substituted or unsubstituted heteroaryl group with 3-30 carbon atoms, a substituted or unsubstituted aryl group with 6-30 carbon atoms;
  • the substituents on L and Ar are one or more, and the substituents in Ar and L are the same or different from each other, and are each independently selected from deuterium, halogen group, cyano group, and the number of carbon atoms is 6-20
  • the two substituents connected to the same atom can be connected to each other to form a saturated or unsaturated 5- to 13-membered aliphatic ring with the atoms connected to them. Or 5-13 membered aromatic ring.
  • substitution in the substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms means being selected from: fluorine, deuterium, cyano, trifluoromethyl, trimethylsilyl, methyl Substituents of phenyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexane, phenyl, naphthyl, and pyridyl.
  • the substituents on L when there are multiple substituents on L, the substituents on L may be the same or different, and when there are multiple substituents on Ar, the substituents on Ar may be the same or different.
  • L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 14 carbon atoms.
  • the substituents in L are each independently selected from the group consisting of deuterium, fluorine, chlorine, bromine, cyano, alkyl groups having 1 to 4 carbon atoms, haloalkyl groups having 1 to 4 carbon atoms, and 3 to 4 carbon atoms.
  • two substituents connected to the same atom can be connected to each other to form a saturated or unsaturated 5- to 13-membered aliphatic ring or 5- to 13-membered aromatic ring.
  • the L is selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted phenylene Substituted naphthylene, substituted or unsubstituted 9,9-dimethylfluorenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted 9,9-dimethyl-9H-9-silyl Fluorene subunits, substituted or unsubstituted dibenzofuran subunits, substituted or unsubstituted dibenzothiophene subunits, substituted or unsubstituted quinolinylene, substituted or unsubstituted isoquinolinylene, substituted or Unsubstituted carbazolylidene, substituted or unsubstituted phenanthrylene, substituted
  • L is selected from a single bond or a group consisting of groups represented by chemical formula j-1 to chemical formula j-13:
  • M 2 is selected from a single bond or
  • Q 1 to Q 5 are each independently selected from N or C(J 5 ), and at least one of Q 1 to Q 5 is selected from N; when two or more of Q 1 to Q 5 are selected from C(J 5 ), any two J 5 are the same or different;
  • Q 6 to Q 13 are each independently selected from N or C(J 6 ), and at least one of Q 6 to Q 13 is selected from N; when two or more of Q 6 to Q 13 are selected from C(J 6 ), any two J 6 are the same or different;
  • Q 14 to Q 23 are each independently selected from N, C or C (J 7 ), and at least one of Q 14 to Q 23 is selected from N; when two or more of Q 14 to Q 23 are selected from C (J 7 ), any two J 7s are the same or different;
  • Q 24 to Q 33 are each independently selected from N, C or C (J 8 ), and at least one of Q 24 to Q 33 is selected from N; when two or more of Q 24 to Q 33 are selected from C (J 8 ), any two J 8s are the same or different;
  • E 1 to E 14 and J 5 to J 8 are each independently selected from: hydrogen, deuterium, halogen group, cyano group, heteroaryl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms , Trialkylsilyl groups with 3-9 carbon atoms, arylsilyl groups with 8-12 carbon atoms, alkyl groups with 1-10 carbon atoms, haloalkyl groups with 1-10 carbon atoms , C 3-10 cycloalkyl, C 2-10 heterocycloalkyl, C 4-10 heterocycloalkenyl, C 1-10 alkoxy , Alkylthio groups having 1 to 10 carbon atoms, aryloxy groups having 6 to 18 carbon atoms, and arylthio groups having 6 to 18 carbon atoms;
  • E r represents any integer of 1 to 14, E r E r represents the number of substituents; when r is selected from 1,2, When 3, 4, 5, 6, 9, 13, or 14, e r is selected from 1, 2, 3 or 4; when r is selected from 7 or 11, e r is selected from 1, 2, 3, 4, 5 or 6; when r is 12, e r is selected from 1, 2, 3, 4, 5, 6 or 7; when r is selected from 8 or 10, e r is selected from 1, 2, 3, 4, 5, 6 , 7 or 8; when e r is greater than 1, any two E r are the same or different;
  • K 3 is selected from O, S, Se, N (E 15 ), C (E 16 E 17 ), Si (E 18 E 19 ); wherein each of E 15 , E 16 , E 17 , E 18 and E 19 are respectively Independently selected from: hydrogen, aryl groups having 6 to 20 carbon atoms, heteroaryl groups having 3 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and rings having 3 to 10 carbon atoms alkyl;
  • E 16 and E 17 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
  • E 18 and E 19 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
  • Each K 4 is independently selected from a single bond, O, S, Se, N (E 20 ), C (E 21 E 22 ), Si (E 23 E 24 ); wherein, each of E 20 , E 21 , E 22 , E 23 and E 24 are each independently selected from: hydrogen, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and the number of carbon atoms It is a cycloalkyl group of 3-10, a heterocycloalkyl group of 2-10 carbon atoms;
  • E 21 and E 22 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
  • E 23 and E 24 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms with which they are commonly connected.
  • L is When M 2 and K 4 are single bonds, E 11 are both hydrogen, and K 3 is C (E 16 E 17 ), optionally, E 16 and E 17 connected to the same atom are connected to each other with The atoms they connect together form a saturated or unsaturated 5- to 13-membered aliphatic ring means that E 16 and E 17 can be connected to each other to form a 5- to 13-membered ring, or they can exist independently of each other; when E 16 and E 17 form In the case of an aliphatic ring, the number of atoms of the ring can be a 5-membered ring, for example It can also be a 6-membered ring, for example It can also be a 10-membered ring, for example Of course, the number of atoms in the ring formed by the interconnection of E 16 and E 17 can also be other values, which will not be listed here.
  • the ring formed by the interconnection of E 16 and E 17 can also be an aromatic ring, such as a 13-membered aromatic ring,
  • E 18 and E 19 are connected to each other to form a 5- to 13-membered aliphatic ring or aromatic ring with the atoms they are commonly connected to have the same meaning as E 16 and E 17 .
  • E 21 and E 22 are connected to each other to form a 5- to 13-membered aliphatic ring or 5- to 13-membered aromatic ring with the atoms they are commonly connected to have the same meaning as E 16 and E 17 .
  • E 23 and E 24 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to have the same meaning as E 16 and E 17 .
  • only one of Q 1 to Q 5 is selected from N.
  • only one of Q 6 to Q 13 is selected from N.
  • only one of Q 14 to Q 23 is selected from N.
  • only one of Q 24 to Q 33 is selected from N.
  • L is selected from the group consisting of a single bond, unsubstituted L 1 , and substituted L 1 , wherein the unsubstituted L 1 is selected from the group consisting of:
  • the substituted L 1 is unsubstituted L 1 with one or more selected from deuterium, fluorine, chlorine, bromine, cyano, alkyl having 1 to 4 carbon atoms, and haloalkane having 1 to 4 carbon atoms Group, trialkylsilyl group with 3 to 9 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, aryl group with 6 to 15 carbon atoms, and heteroaryl group with 3 to 12 carbon atoms
  • the group formed by substitution, and when the number of substituents on the substituted L 1 is more than one, any two substituents are the same or different.
  • the above-mentioned substituted L 1 is unsubstituted L 1 with 0, 1, 2, 3 or 4 selected from deuterium, fluorine, chlorine, bromine, cyano, methyl, ethyl, propyl, tert-butyl , Phenyl, biphenyl, naphthyl, pyridyl, carbazolyl, dibenzothienyl, and dibenzofuranyl substituents, and when the substituents on the substituted L 1 When the number is plural, any two substituents are the same or different.
  • said L is a single bond or any one of the following groups:
  • said L is a single bond or any one of the following groups:
  • Ar is selected from the group consisting of groups represented by chemical formula i-1 to chemical formula i-18:
  • M 1 is selected from a single bond or
  • G 1 to G 5 are each independently selected from N or C(F 1 ), and at least one of G 1 to G 5 is selected from N; when two or more of G 1 to G 5 are selected from C(F 1 ) , Any two F 1 are the same or different;
  • G 6 to G 13 are each independently selected from N or C(F 2 ), and at least one of G 6 to G 13 is selected from N; when two or more of G 6 to G 13 are selected from C(F 2 ) , Any two F 2 are the same or different;
  • G 14 to G 23 are each independently selected from N or C(F 3 ), and at least one of G 14 to G 23 is selected from N; when two or more of G 14 to G 23 are selected from C(F 3 ) , Any two F 3 are the same or different; or, optionally, two adjacent F 3 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring;
  • G 24 to G 33 are each independently selected from N or C(F 4 ), and at least one of G 24 to G 33 is selected from N; when two or more of G 24 to G 33 are selected from C(F 4 ) , Any two F 4 are the same or different; or, optionally, two adjacent F 4 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring;
  • G 34 to G 37 are each independently selected from N or C(F 5 ), and when two or more of G 34 to G 37 are selected from C(F 5 ), any two F 5s are the same or different; or, Optionally, two adjacent F 5s are connected to each other to form a 5- to 10-membered aromatic ring or a 5- to 10-membered heteroaromatic ring;
  • G 38 to G 45 are each independently selected from N or C(F 6 ), and at least one of G 38 to G 45 is selected from N; when two or more of G 38 to G 45 are selected from C(F 6 ) , Any two F 6 are the same or different;
  • G 46 to G 53 are each independently selected from N or C(F 7 ), and at least one of G 46 to G 53 is selected from N; when two or more of G 46 to G 53 are selected from C(F 7 ), any two F 7s are the same or different; or, optionally, two adjacent F 7s are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring.
  • two adjacent F 5 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring
  • G 34 and G 35 are both CH
  • G 36 and G 37 are both C(F 5 ) and both form a 6-membered aromatic ring
  • formula i-16 is The ring formation of adjacent F 5 can also be the formation of other aromatic or heteroaromatic rings, which will not be listed here.
  • two adjacent F 3 , F 4 or F 7 are connected to each other to form a ring with the same meaning, and will not be listed one by one.
  • D 1 is selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and those having 1 to 10 carbon atoms A halogenated alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms;
  • D 2 to D 9 and D 21 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl having 3 to 12 carbon atoms, and alkane having 1 to 10 carbon atoms Group, halogenated alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 10 carbon atoms, carbon Alkylthio groups having 1 to 10 atoms, heteroaryl groups having 3 to 18 carbon atoms;
  • D 10 to D 20 and F 1 to F 7 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, and 1 to carbon atoms 10 alkyl groups, halogenated alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkyl sulfides with 1 to 10 carbon atoms Group, optionally with 0, 1, 2 or 3 selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, carbon atom Alkylamino group with 1 to 6, cycloalkyl with 3 to 7 carbon atoms, aryl with 6 to 15 carbon atoms, heteroaryl with 3 to 12 carbon atoms, 1 carbon atom ⁇ 4 alkoxy group, C 1-4 haloalkyl group, C 3
  • d 1 ⁇ d 21 are represented by d k
  • D 1 ⁇ D 21 are represented by D k
  • k is a variable, representing any integer from 1 to 21
  • d k is the number of substituents D k ; wherein, when k is selected from 5 Or when 17, d k is selected from 1, 2 or 3; when k is selected from 2, 7, 8, 12, 15, 16, 18 or 21, d k is selected from 1, 2, 3 or 4; when k is selected When from 1, 3, 4, 6, 9 or 14, d k is selected from 1, 2, 3, 4 or 5; when k is 13, d k is selected from 1, 2, 3, 4, 5 or 6; When k is selected from 10 or 19, d k is selected from 1, 2, 3, 4, 5, 6 or 7; when k is 20, d k is selected from 1, 2, 3, 4, 5, 6, 7 Or 8; when k is 11, d k is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; and when d k is greater than 1, any two D k are the same or different;
  • K 1 and K 6 are independently selected from O, S, N (D 22 ), C (D 23 D 24 ), Si (D 28 D 29 ); wherein, each of D 22 , D 23 , D 24 , D 28 , D 29 are independently selected from: aryl groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or 3 to 10 carbon atoms ⁇ cycloalkyl;
  • D 23 and D 24 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
  • D 28 and D 29 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
  • K 2 is selected from single bond, O, S, N (D 25 ), C (D 26 D 27 ), Si (D 30 D 31 ); wherein, each of D 25 , D 26 , D 27 , D 30 , D 31 They are independently selected from: aryl groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkanes having 3 to 10 carbon atoms base,
  • D 26 and D 27 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
  • the above-mentioned D 30 and D 31 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
  • K 5 is selected from O, S, Se, N(D 32 ), C(D 33 D 34 ), wherein D 32, D 33 and D 34 are each independently selected from: aryl groups having 6 to 18 carbon atoms , Heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 3 to 10 carbon atoms.
  • D 23 and D 24 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms connected to them" means that D 23 and D 24 may be connected to each other to form one Rings can also exist independently of each other.
  • the ring can be a 5-membered aliphatic Family ring, for example It can also be a 6-membered aliphatic ring, for example It can be a 13-membered aromatic ring, for example It can also be a 14-membered heteroaromatic ring, for example
  • the number of carbon atoms in the ring formed by the interconnection of D 23 and D 24 can also be other values, which will not be listed here.
  • D 26 and D 27 are connected to each other to form a 5- to 14-membered aliphatic ring or aromatic ring with the atoms they are commonly connected to have the same meaning as D 23 and D 24.
  • D 28 and D 29 , D 26 and D 27 , D 30 and D 31 are connected to each other to form a 5- to 14-membered aliphatic or aromatic ring with the same meaning as D 23 and D 24 same.
  • At least two of G 1 to G 5 are selected from N.
  • At least two of G 6 to G 13 are selected from N.
  • At least two of G 14 to G 23 are selected from N.
  • At least two of G 24 to G 33 are selected from N.
  • At least two of G 38 to G 45 are selected from N.
  • At least two of G 46 to G 53 are selected from N.
  • Ar is selected from substituted or unsubstituted aryl groups with 6 to 25 carbon atoms, substituted or unsubstituted heteroaryl groups with 3 to 25 carbon atoms; substitution on Ar One or more groups, the same or different from each other, and each independently selected from deuterium, fluorine, chlorine, cyano, aryl groups with 6 to 12 carbon atoms, and substituted or unsubstituted with 3 to 18 carbon atoms Heteroaryl groups, alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms , Cycloalkyl groups with 5 to 10 carbon atoms, trialkylsilyl groups with 3 to 9 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, and arylthio groups with 6 to 20 carbon atoms And an aryls
  • substitution in the substituted or unsubstituted heteroaryl group having 3 to 18 carbon atoms means being selected from: fluorine, deuterium, cyano, trifluoromethyl, trimethylsilyl, methyl Substituents of phenyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexane, phenyl, naphthyl, and pyridyl.
  • Ar is selected from unsubstituted Ar 1 or substituted Ar 1 , wherein the unsubstituted Ar 1 is selected from the group consisting of the following groups:
  • Z 1 and Z 2 are each independently selected from hydrogen, an aryl group with 6 to 20 carbon atoms, and a heteroaryl group with 3 to 20 carbon atoms; any two Z 1s are the same or different, any two Z 2 is the same or different;
  • the substituted Ar 1 is unsubstituted Ar 1 with one or more selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 4 carbon atoms, and alkoxy with 1 to 4 carbon atoms. , Alkylamino groups with 1 to 4 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, heteroaryl groups with 3 to 12 carbon atoms, carbon atoms A group formed by the substitution of alkylthio groups having 1 to 4, haloalkyl groups having 1 to 4 carbon atoms, and alkylsilyl groups having 3 to 9 carbon atoms, and when the substituents on Ar 1 are When the number is more than one, any two substituents are the same or different.
  • substituted Ar 1 means that the unsubstituted Ar 1 is substituted by one or more substituents, and the substituents can replace the hydrogen atom at any position in the unsubstituted Ar 1 described above, for example, Is any hydrogen atom in the substituent group Z 1.
  • the substituted Ar 1 is unsubstituted Ar 1 with one or more selected from deuterium, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy Group, isopropoxy, cyclopentyl, cyclohexyl, phenyl, naphthyl, pyridyl, trifluoromethyl, trimethylsilyl, and when the substituent on Ar 1 is When the number is more than one, any two substituents are the same or different.
  • Ar is selected from unsubstituted Ar 1 or substituted Ar 1 , wherein the unsubstituted Ar 1 is also selected from the group consisting of the following groups:
  • the substituted Ar 1 is unsubstituted Ar 1 with one or more selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 4 carbon atoms, and alkoxy with 1 to 4 carbon atoms.
  • Z 1 and Z 2 are each independently selected from: hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or Unsubstituted perylene, substituted or unsubstituted fluoranthene, substituted or unsubstituted Group, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, Substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted carbazol-9-ylphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted
  • the substituents in Z 1 and Z 2 are each independently selected from: fluorine, deuterium, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy , Ethoxy, isopropoxy, trifluoromethyl, cyclopentyl, cyclohexane, phenyl, naphthyl, pyridyl, pyrimidinyl, quinolyl, isoquinolyl. It should be noted that when Z 1 or Z 2 is hydrogen, the hydrogen atom may be substituted for the hydrogen atom to be connected to Ar 1 without positioning the bonding bond. E.g, Include
  • Ar may be selected from aryl groups or electron-rich heteroaryl groups.
  • the heteroatoms on the electron-rich heteroaryl groups can increase the electron cloud density of the conjugated system of the heteroaryl group as a whole instead of reducing the heteroaryl group.
  • the electron cloud density of the conjugated system of the aryl group for example, the lone pair of electrons on the heteroatom can participate in the conjugated system to increase the electron cloud density of the conjugated system of the heteroaryl group.
  • electron-rich heteroaryl groups may include, but are not limited to, carbazolyl, dibenzofuranyl, dibenzothiazolyl, furanyl, pyrrolyl, and the like.
  • the nitrogen-containing compound Since both the aryl group and the electron-rich heteroaryl group can effectively enhance the electron cloud density of the nitrogen-containing compound and can adjust the HOMO energy level of the nitrogen-containing compound, the nitrogen-containing compound will have better hole transport ability.
  • the nitrogen-containing compound can be used as the host material of the hole-type organic light-emitting layer, and cooperate with the host material of the electron-type organic light-emitting layer for transporting electrons to form the host material of the organic light-emitting layer.
  • Ar is selected from the following structures:
  • Ar is an electron-deficient heteroaryl group (also known as an electron-poor heteroaryl group), on which heteroatoms can reduce the electron cloud density of the heteroaryl conjugate system as a whole instead of increasing the heteroaryl group.
  • the electron cloud density of the conjugated system of the aryl group for example, the lone pair of electrons on the heteroatom does not participate in the conjugated system, and the electron cloud density of the conjugated system is reduced due to the strong electronegativity of the heteroatom.
  • electron-deficient heteroaryl groups may include, but are not limited to, pyridinyl, pyrimidinyl, s-triazinyl, quinolinyl, isoquinolinyl, benzopyrazolyl, benzimidazolyl, quinoxalinyl, Phenanthroline and so on.
  • Ar can form the electron transport core group of the nitrogen-containing compound, so that the nitrogen-containing compound can effectively realize electron transport, and can effectively balance the transmission rate of electrons and holes in the organic light-emitting layer.
  • the nitrogen-containing compound can be used as the host material of the bipolar organic light-emitting layer to simultaneously transport electrons and holes, or can be used as the host material of the electron-type organic light-emitting layer to cooperate with the host material of the hole-type organic light-emitting layer.
  • Ar is selected from the following structures:
  • R 1 , R 2 , R 3 , and R 4 are the same or different from each other, and are each independently selected from deuterium, halogen group, cyano group, halogenated alkyl group having 1 to 4 carbon atoms, carbon Alkyl groups having 1 to 4 atoms, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, 4 to carbon atoms 6 heterocycloalkyl groups, alkoxy groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms, trialkylsilyl groups having 3 to 9 carbon atoms, 6 carbon atoms -15 aryl groups, heteroaryl groups having 3 to 12 carbon atoms, aryloxy groups having 6 to 15 carbon atoms, arylthio groups having 6 to 15 carbon atoms, and triphenylsilyl groups.
  • R 1 , R 2 , R 3 , R 4 are the same or different from each other, and are each independently selected from deuterium, fluorine, chlorine, bromine, cyano, methyl, isopropyl, ethyl Isopropyl, cyclopropyl, tert-butyl, ethoxy, trifluoromethyl, trimethylsilyl, phenyl, pyridyl, dimethylfluorenyl, dibenzofuranyl, dibenzothienyl , Pyrimidinyl, triazinyl, triphenylsilyl, n 1 , n 2 , n 3 , and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4, respectively.
  • the nitrogen-containing compound is selected from the group consisting of the following compounds:
  • the present application also provides an organic electroluminescent device.
  • the organic electroluminescent device includes an anode and a cathode disposed oppositely, and a functional layer disposed between the anode and the cathode, and the functional layer includes a hole injection layer , Hole transport layer, organic light emitting layer, electron transport layer and electron injection layer; the organic light emitting layer contains the above-mentioned nitrogen-containing compound to improve the voltage characteristics, efficiency characteristics and life characteristics of the organic electroluminescent device.
  • an organic electroluminescent device may include an anode 100, a hole transport layer 321, an organic light emitting layer 330, an electron transport layer 340, and a cathode 200 which are sequentially stacked.
  • the nitrogen-containing compound provided in this application can be applied to the organic light-emitting layer 330 of an organic electroluminescent device to increase the life of the organic electroluminescent device, increase the luminous efficiency of the organic electroluminescent device, or reduce the driving voltage of the organic electroluminescent device .
  • the anode 100 includes an anode material, which is optionally a material with a large work function (work function) that facilitates injection of holes into the functional layer.
  • anode materials include, but are not limited to: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combined metals and oxides such as ZnO: Al or SnO 2 : Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-di (Oxy)thiophene] (PEDT), polypyrrole and polyaniline.
  • a transparent electrode containing indium tin oxide (ITO) as the anode is included.
  • the hole transport layer 321 may include one or more hole transport materials, and the hole transport materials may be selected from carbazole polymers, carbazole-linked triarylamine compounds or other types of compounds. This does not make special restrictions.
  • the organic light-emitting layer 330 may include a host material and a guest material.
  • the holes injected into the organic light-emitting layer 330 and the electrons injected into the organic light-emitting layer 330 can recombine in the organic light-emitting layer 330 to form excitons, and the excitons transfer energy to The host material, the host material transfers energy to the guest material, so that the guest material can emit light.
  • the host material may be composed of the nitrogen-containing compound of the present application, especially a nitrogen-containing compound containing an electron-deficient aromatic heterocycle in the W group.
  • nitrogen-containing compounds can transport electrons and holes at the same time, and can balance the transmission efficiency of holes and electrons. Therefore, electrons and holes can be efficiently recombined in the organic light-emitting layer to improve the light-emitting efficiency of the organic electroluminescent device.
  • the host material may be a composite material, for example, may include the nitrogen-containing compound of the present application and the host material of the electronic organic light-emitting layer.
  • the nitrogen-containing compound of the present application can effectively transport holes, so that the hole transport efficiency is balanced with the electron transport efficiency of the organic light-emitting layer, so that electrons and holes can be efficiently recombined in the organic light-emitting layer, and the organic electroluminescent device is improved The luminous efficiency.
  • the host material may include the nitrogen-containing compound of the present application and GH-n1.
  • the guest material of the organic light-emitting layer 330 may be a compound with a condensed aryl group or its derivative, a compound with a heteroaryl group or its derivative, an aromatic amine derivative, or other materials, which are not particularly limited in this application. .
  • the guest material of the organic light-emitting layer 330 may be Ir(piq) 2 (acac) or the like.
  • the guest material of the organic light-emitting layer 330 may be Ir(ppy) 3 or the like.
  • the electron transport layer 340 can be a single-layer structure or a multi-layer structure, which can include one or more electron transport materials, which can be selected from, but not limited to, benzimidazole derivatives, oxacin Diazole derivatives, quinoxaline derivatives or other electron transport materials.
  • the cathode 200 may include a cathode material, which is a material with a small work function that facilitates injection of electrons into the functional layer.
  • cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or their alloys; or multilayer materials such as LiF/Al , Liq/Al, LiO 2 /Al, LiF/Ca, LiF/Al and BaF 2 /Ca.
  • a metal electrode containing aluminum is included as a cathode.
  • the material of the cathode 200 may be a magnesium-silver alloy.
  • a hole injection layer 310 may be further provided between the anode 100 and the hole transport layer 321 to enhance the ability of injecting holes into the first hole transport layer 321.
  • the hole injection layer 310 can be selected from benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives or other materials, which are not particularly limited in this application.
  • the hole injection layer 310 may be composed of F4-TCNQ.
  • an electron blocking layer 322 may be further provided between the hole transport layer 321 and the organic light-emitting layer 330 to block electrons from being transported to the hole transport layer 321 side, and improve electrons and holes in the organic
  • the recombination rate of the light-emitting layer 330 protects the hole transport layer 321 from the impact of electrons.
  • the material of the electron blocking layer 322 may be a carbazole polymer, a carbazole-linked triarylamine compound, or other feasible structures.
  • an electron injection layer 350 may be further provided between the cathode 200 and the electron transport layer 340 to enhance the ability to inject electrons into the electron transport layer 340.
  • the electron injection layer 350 may include inorganic materials such as alkali metal sulfides and alkali metal halides, or may include complexes of alkali metals and organic substances.
  • the electron injection layer 350 may include LiQ.
  • the present application also provides an electronic device 400.
  • the electronic device 400 includes any of the organic electroluminescent devices described in the foregoing organic electroluminescent device embodiments.
  • the electronic device 400 may be a display device, a lighting device, an optical communication device or other types of electronic devices, such as but not limited to computer screens, mobile phone screens, televisions, electronic paper, emergency lighting, light modules, etc. Since the electronic device 400 has any one of the organic electroluminescent devices described in the foregoing organic electroluminescent device embodiments, it has the same beneficial effects, which will not be repeated here in this application.
  • Anhydrous tetrahydrofuran, dioxane, toluene, ether and other anhydrous solvents are obtained by refluxing and drying of sodium metal.
  • Anhydrous dichloromethane and chloroform are obtained by refluxing and drying with calcium hydride.
  • Ethyl acetate, petroleum ether, n-hexane, N,N-dimethylacetamide and N,N-dimethylformamide are used after being dried in advance with anhydrous sodium sulfate.
  • reaction in each synthesis example is generally carried out under a positive pressure of nitrogen or argon, or a drying tube is placed on an anhydrous solvent (unless otherwise stated); during the reaction, the reaction flask is plugged with a suitable rubber stopper, The substrate is injected into the reaction flask via a syringe. All glassware used is dried.
  • the chromatographic column was a silica gel column, and silica gel (300-400 mesh) was purchased from Qingdao Ocean Chemical Factory.
  • MS mass spectrometry
  • Proton nuclear magnetic resonance spectrum Bruker 400MHz nuclear magnetic instrument, at room temperature, with CD 2 Cl 2 as the solvent (in ppm), and TMS (0 ppm) as the reference standard. When multiple peaks appear, the following abbreviations will be used: s (singlet, singlet), d (doublet, doublet), t (triplet, triplet), m (multiplet, multiplet).
  • the target compound uses Agilent 1260pre-HPLC or Calesep pump 250pre-HPLC (column model: NOVASEP50/80mm DAC), with UV detection at 210nm/254nm.
  • the mixture was stirred and heated to 100°C and reacted for 12 hours; after the reaction, it was cooled to room temperature and filtered The filter cake was rinsed with water and ethanol, and dried to obtain a crude product; the crude product was purified by recrystallization using a toluene/n-heptane system to obtain a pale yellow solid compound 26 (5.2 g; yield 60%).
  • the anode is prepared by the following process: the thickness of ITO is
  • the ITO substrate is cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (thickness), and the photolithography process is used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns, and can use ultraviolet ozone and O 2 :N 2 plasma is used for surface treatment to increase the work function of the anode, and organic solvents can be used to clean the surface of the ITO substrate to remove impurities and grease on the surface of the ITO substrate.
  • the ITO substrate can also be cut into other sizes according to actual needs, and the size of the ITO substrate in this application is not specifically limited here.
  • F4-TCNQ was vacuum evaporated on the experimental substrate (anode) to form a thickness of The hole injection layer (HIL), and HT-01 is vapor-deposited on the hole injection layer to form a thickness of The first hole transport layer.
  • HIL hole injection layer
  • the compound 2: GH-n1: Ir(ppy) 3 was co-evaporated at a ratio of 50%: 45%: 5% (evaporation rate) to form a thickness of The green light-emitting layer (EML).
  • ET-01 and LiQ were mixed at a weight ratio of 1:1 and evaporated to form Thick electron transport layer (ETL), LiQ is vapor-deposited on the electron transport layer to form a thickness of The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at an evaporation rate of 1:9, and then vacuum-evaporated on the electron injection layer to form a thickness of The cathode.
  • ETL Thick electron transport layer
  • EIL electron injection layer
  • Mg magnesium
  • Ag silver
  • the vapor deposition thickness on the above cathode is CP-01 to form an organic cover layer (CPL), thereby completing the manufacture of organic light-emitting devices.
  • Example 2 Except that the compound shown in the column of compound N in Table 10 was used instead of compound 2 in Example 1, the same method as in Example 1 was used to prepare an organic electroluminescent device.
  • compound N is compound 6, and compound 6 is used instead of compound 2 in Example 1 to prepare an organic electroluminescence device.
  • the compound AD shown in the following table replaces the compound 2 in Example 1, and the organic electroluminescent device is prepared by the same method as in Example 1.
  • compound A: GH-n1: Ir(ppy) 3 50%: 45%: 5%.
  • the organic electroluminescent devices prepared in Examples 1 to 16 have similar luminous efficiency under the premise of similar driving voltages. With a certain improvement, the life of the device has been increased by at least 50%. Therefore, when the nitrogen-containing compound of the present application is used as an organic light-emitting layer material of an organic electroluminescence device, especially when used as a host material of an organic light-emitting layer of an organic electroluminescence device, the efficiency performance of the organic electroluminescence device can be improved And longevity.
  • Example 17 Red organic electroluminescent device
  • the anode is prepared by the following process: the thickness of ITO is
  • the ITO substrate is cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (thickness), and the photolithography process is used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns, and can use ultraviolet ozone and O 2 :N 2 plasma is used for surface treatment to increase the work function of the anode, and organic solvents can be used to clean the surface of the ITO substrate to remove impurities and grease on the surface of the ITO substrate.
  • the ITO substrate can also be cut into other sizes according to actual needs, and the size of the ITO substrate in this application is not specifically limited here.
  • F4-TCNQ was vacuum-evaporated on the experimental substrate (anode) to form a thickness of The hole injection layer (HIL), and HT-01 is vapor-deposited on the hole injection layer to form a thickness of The first hole transport layer.
  • HIL hole injection layer
  • compound 26 Ir(piq) 2 (acac) was co-evaporated at a ratio of 95%: 5% (evaporation rate) to form a thickness of The red light-emitting layer (EML).
  • EML red light-emitting layer
  • ET-01 and LiQ were mixed at a weight ratio of 1:1 and evaporated to form Thick electron transport layer (ETL), LiQ is vapor-deposited on the electron transport layer to form a thickness of The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at an evaporation rate of 1:9, and then vacuum-evaporated on the electron injection layer to form a thickness of The cathode.
  • ETL Thick electron transport layer
  • EIL electron injection layer
  • Mg magnesium
  • Ag silver
  • the vapor deposition thickness on the above cathode is CP-01 to form an organic cover layer (CPL), thereby completing the manufacture of organic light-emitting devices.
  • Example 17 Except that the compound EH shown in the following table replaced compound 26 in Example 17 when forming the light-emitting layer, the same method as in Example 17 was used to prepare an organic electroluminescent device.
  • the driving voltage and luminous efficiency of the organic electroluminescent devices prepared in Examples 17-29 have been improved to a certain extent.
  • the luminous efficiency of the device is increased by at least 10%, and the life span is increased by at least 27%. Therefore, when the nitrogen-containing compound of the present application is used as an organic light-emitting layer material of an organic electroluminescence device, especially when used as a host material of an organic light-emitting layer of an organic electroluminescence device, the efficiency performance of the organic electroluminescence device can be improved And life performance.
  • the adamantane spiro-fused fluorenyl group which is part of the core of the nitrogen-containing compound, is connected to the carbazolyl group, so that the compound as a whole has strong rigidity and the nitrogen-containing compound of the present application has a high first three
  • the carbazole ring conjugated to the fused fluorenyl group in the compound has a good hole transport ability, so the nitrogen-containing compound of the present application is suitable as the host material of the light-emitting layer in the organic electroluminescence device.
  • Nitrogen-containing compounds have high hole mobility, help promote the balance of hole and electron transport in the light-emitting layer, and improve the efficiency performance of organic electroluminescent devices.
  • the recombination rate of electrons and holes in the organic light-emitting layer is increased, which reduces or prevents electrons from passing through the organic light-emitting layer to the hole transport layer, thereby effectively protecting the hole transport layer material from the impact of electrons and improving the organic electricity.
  • the lifetime of the electroluminescent device is increased, which reduces or prevents electrons from passing through the organic light-emitting layer to the hole transport layer, thereby effectively protecting the hole transport layer material from the impact of electrons and improving the organic electricity.

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Abstract

The present application provides a nitrogen containing compound, an organic electroluminescent device using same, and an electronic device. A chemical structure of an organic compound in the present invention comprises a carbazole ring. The organic compound can be used as the material of a light-emitting layer in an electroluminescent device to improve the efficiency of the organic electroluminescent device and prolong the service life thereof.

Description

含氮化合物、使用其的有机电致发光器件及电子装置Nitrogen-containing compound, organic electroluminescence device and electronic device using the same
相关申请的交叉引用Cross-references to related applications
本发明要求于2020年4月7日递交的、申请号为CN 202010266202.6的中国专利申请的优先权，在此引用上述中国专利申请公开的内容全文以作为本公开的一部分。The present invention claims the priority of the Chinese patent application filed on April 7, 2020 with the application number CN 202010266202.6, and the full content of the Chinese patent application disclosed above is cited here as a part of this disclosure.
本发明要求于2020年8月10日递交的、申请号为CN 202010798721.7的中国专利申请的优先权，在此引用上述中国专利申请公开的内容全文以作为本公开的一部分。The present invention claims the priority of the Chinese patent application filed on August 10, 2020 with the application number CN 202010798721.7, and the full content of the Chinese patent application disclosed above is cited here as a part of this disclosure.
技术领域Technical field
本发明属于有机电致发光材料技术领域，具体涉及一种含氮化合物、使用其的有机电致发光器件及电子装置。The invention belongs to the technical field of organic electroluminescent materials, and specifically relates to a nitrogen-containing compound, an organic electroluminescent device and an electronic device using the nitrogen-containing compound.
背景技术Background technique
有机电致发光器件，例如有机发光二极管(OLED)，通常包括相对设置的阴极和阳极，以及设置于阴极和阳极之间的功能层。该功能层由多层有机或者无机膜层组成，且一般包括有机发光层、位于有机发光层与阳极之间的空穴传输层、位于有机发光层与阴极之间的电子传输层。当阴阳两极施加电压时，两电极产生电场，在电场的作用下，阴极侧的电子向电致发光层移动，阳极侧的空穴也向发光层移动，电子和空穴在电致发光层结合形成激子，激子处于激发态向外释放能量，进而使得电致发光层对外发光。An organic electroluminescent device, such as an organic light emitting diode (OLED), usually includes a cathode and an anode disposed opposite to each other, and a functional layer disposed between the cathode and the anode. The functional layer is composed of multiple organic or inorganic film layers, and generally includes an organic light-emitting layer, a hole transport layer between the organic light-emitting layer and the anode, and an electron transport layer between the organic light-emitting layer and the cathode. When voltage is applied to the cathode and anode, the two electrodes generate an electric field. Under the action of the electric field, the electrons on the cathode side move to the electroluminescent layer, the holes on the anode side also move to the light emitting layer, and the electrons and holes are combined in the electroluminescent layer. Excitons are formed, and the excitons are in an excited state to release energy to the outside, so that the electroluminescent layer emits light to the outside.
现有技术中，CN104039778A等公开了可以在有机电致发光器件中制备发光层的材料。但是目前的有机电致发光材料依然存在发光寿命短、发光效率低的问题。因此，有必要继续研发新型的材料，以进一步提高有机电致发光器件的寿命和效率性能。In the prior art, CN104039778A, etc. disclose materials that can be used to prepare a light-emitting layer in an organic electroluminescent device. However, current organic electroluminescent materials still have the problems of short luminous life and low luminous efficiency. Therefore, it is necessary to continue to develop new materials to further improve the life and efficiency performance of organic electroluminescent devices.
发明内容Summary of the invention
本发明的目的在于提供一种性能优异的有机电致发光材料，可用作有机电致发光器件中的发光层层。The purpose of the present invention is to provide an organic electroluminescent material with excellent performance, which can be used as a light-emitting layer in an organic electroluminescent device.
为了实现上述目的，本发明提供一种含氮化合物，所述含氮化合物的结构式如化学式(1)所示：In order to achieve the above objective, the present invention provides a nitrogen-containing compound, the structural formula of the nitrogen-containing compound is shown in the chemical formula (1):
Figure PCTCN2020122273-appb-000001
Figure PCTCN2020122273-appb-000001
其中，环A为成环碳原子数为10～14的稠合芳环或成环碳原子数为8～12的稠合杂芳环，且所述环A不是咔唑环；Wherein, ring A is a fused aromatic ring with 10 to 14 carbon atoms or a fused heteroaromatic ring with 8 to 12 carbon atoms, and the ring A is not a carbazole ring;
环B为苯环、成环碳原子数为10～14的稠合芳环或成环碳原子数为8～12的稠合杂芳环；Ring B is a benzene ring, a fused aromatic ring with 10 to 14 carbon atoms, or a fused heteroaromatic ring with 8 to 12 carbon atoms;
环C为苯环或成环碳原子数为10～14的稠合芳环；Ring C is a benzene ring or a condensed aromatic ring with 10-14 carbon atoms;
R 1、R 2、R 3、R 4彼此相同或不同，且分别独立地选自氘、卤素基团、氰基、碳原子数为1～12的卤代烷基、碳原子数为1～12的烷基、碳原子数为2～10的烯基、碳原子数为2～10的炔基、碳原子数为3～12的环烷基、碳原子数为2～10的杂环烷基、碳原子数为1～12的烷氧基、碳原子数为1～12的烷硫基、碳原子数为3～12的三烷基硅基、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基、碳原子数为6～20的芳氧基、碳原子数为6～20的芳硫基、碳原子数为6～18的芳基甲硅烷基； R 1 , R 2 , R 3 , and R 4 are the same or different from each other and are each independently selected from deuterium, halogen group, cyano group, halogenated alkyl group having 1 to 12 carbon atoms, and one having 1 to 12 carbon atoms Alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, heterocycloalkyl groups having 2 to 10 carbon atoms, Alkoxy groups having 1 to 12 carbon atoms, alkylthio groups having 1 to 12 carbon atoms, trialkylsilyl groups having 3 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, carbon A heteroaryl group having 3 to 20 atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms;
n 1表示取代基R 1的个数，n 2表示取代基R 2的个数，n 3表示取代基R 3的个数，n 4表示取代基R 4的个数，n 1、n 2、n 3、n 4彼此相同或者不同，且分别独立地选自0、1、2、3或4； n 1 represents the number of substituents R 1 , n 2 represents the number of substituents R 2 , n 3 represents the number of substituents R 3 , n 4 represents the number of substituents R 4 , n 1 , n 2 , n 3 and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4;
当n 1大于1时，任意两个所述R 1相同或者不同，当n 2大于1时，任意两个所述R 2相同或者不同；当n 3大于1时，任意两个所述R 3相同或者不同,当n 4大于1时，任意两个所述R 4相同或者不同； When n 1 is greater than 1, any two of R 1 are the same or different; when n 2 is greater than 1, any two of R 2 are the same or different; when n 3 is greater than 1, any two of R 3 Same or different, when n 4 is greater than 1, any two of the R 4 are the same or different;
W选自碳原子数为6～40的取代或者未取代的芳基、碳原子数为3～40的取代或者未取代的杂芳基；W is selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms;
W中的取代基彼此相同或不同，各自独立地选自如下基团所组成的组：氘，卤素基团，氰基，碳原子数为1～12的烷基，碳原子数为1～12的卤代烷基，碳原子数为3～10的环烷基，碳原子数为2～10的杂环烷基，碳原子数为7～10的芳烷基，碳原子数为4～10的杂芳烷基，任选地被0、1、2或3个选自氘、氟、氯、溴、氰基、烷基的取代基所取代的碳原子数为6～30的芳基，任选地被0、1、2或3个选自氘、氟、氯、溴、氰基、烷基的取代基所取代的碳原子数为3～30的杂芳基，碳原子数为1～12的烷氧基，碳原子数为1～12的烷硫基，碳原子数为3～12的三烷基硅烷基，碳原子数为6～30的芳基甲硅烷基，碳原子数为6～20的芳氧基，碳原子数为6～20的芳硫基；The substituents in W are the same or different, and are independently selected from the group consisting of deuterium, halogen group, cyano group, alkyl group with 1-12 carbon atoms, and 1-12 carbon atoms. The halogenated alkyl group, the cycloalkyl group with 3 to 10 carbon atoms, the heterocycloalkyl group with 2 to 10 carbon atoms, the aralkyl group with 7 to 10 carbon atoms, the heterocyclic alkyl group with 4 to 10 carbon atoms Aralkyl, optionally substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl, aryl groups having 6 to 30 carbon atoms, optionally Heteroaryl groups having 3 to 30 carbon atoms and 1 to 12 carbon atoms substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl The alkoxy group, an alkylthio group having 1 to 12 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and 6 carbon atoms ～20 aryloxy group, arylthio group with 6 to 20 carbon atoms;
在所述W中，当同一原子上具有两个取代基时，任选地，连接于同一原子上的两个取代基之间相互连接以与它们共同连接的原子形成饱和或不饱和的5～18元脂肪族环或5～18元芳香环。In the W, when there are two substituents on the same atom, optionally, the two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5~ 18-membered aliphatic ring or 5-18-membered aromatic ring.
根据本申请的第二个方面，提供一种有机电致发光器件，有机电致发光器件包括相对设置的阳极和阴极，以及设置于所述阳极和所述阴极之间的功能层；所述功能层包含上述的含氮化合物。According to a second aspect of the present application, an organic electroluminescent device is provided. The organic electroluminescent device includes an anode and a cathode disposed oppositely, and a functional layer disposed between the anode and the cathode; the function The layer contains the aforementioned nitrogen-containing compound.
根据本申请的第三个方面，提供一种电子装置，所述电子装置包括有本申请的有机电致发光器件。According to a third aspect of the present application, there is provided an electronic device including the organic electroluminescent device of the present application.
本申请化合物中，作为含氮化合物核心中一部分的金刚烷螺合稠合芴基具有较强的刚性以及第一三重态能级，化合物中与稠合芴基共轭连接的咔唑环具有较好的空穴传输能力，因此本申请的含氮化合物适合作为有机电致发光器件中的发光层主体材料。金刚烷基与芴基螺合，其可以通过超共轭效应而大幅增加大平面共轭结构的电子云密度，增强含氮化合物的空穴迁移率，有助于促进发光层中空穴和电子的传输平衡，改善有机电致发光器件的效率性能。不仅如此，含氮化合物空穴传输性能的提升，可以提高电子和空穴在有机发光层中的复合率，减少或者避免电子穿过有机发光层而向空穴传输层传输，进而可以有效地保护空穴传输层材料免受电子的冲击，提高有机电致发光器件的寿命。不仅如此，螺合于芴基上的金刚烷基具有大的空间体积和较强的刚性，因此其可以降低大平面共轭结构之间的相互作用力，减小分子间π-π堆叠，调节分子间的堆叠程度，进而使得含氮化合物在成膜时能够具有更为稳定的无定形态，改善含氮化合物的成膜性，进而进一步提高有机电致发光器件的寿命。In the compound of the present application, the adamantane spiro-fused fluorenyl group as a part of the core of the nitrogen-containing compound has strong rigidity and the first triplet energy level, and the carbazole ring conjugated to the fused fluorenyl group in the compound has With better hole transport ability, the nitrogen-containing compound of the present application is suitable as the host material of the light-emitting layer in an organic electroluminescent device. The adamantyl group and the fluorenyl group are spiro, which can greatly increase the electron cloud density of the large planar conjugated structure through the hyperconjugation effect, enhance the hole mobility of the nitrogen-containing compound, and help promote the exchange of holes and electrons in the light-emitting layer Transmission balance improves the efficiency performance of organic electroluminescent devices. Not only that, the improvement of the hole transport performance of nitrogen-containing compounds can increase the recombination rate of electrons and holes in the organic light-emitting layer, reduce or prevent electrons from passing through the organic light-emitting layer to the hole transport layer, thereby effectively protecting The hole transport layer material is protected from the impact of electrons, and the life of the organic electroluminescent device is improved. Not only that, the adamantyl group screwed on the fluorene group has a large space volume and strong rigidity, so it can reduce the interaction force between the large plane conjugated structure, reduce the intermolecular π-π stacking, and adjust The degree of intermolecular stacking in turn enables the nitrogen-containing compound to have a more stable amorphous state during film formation, improves the film-forming properties of the nitrogen-containing compound, and further increases the life of the organic electroluminescent device.
本申请的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present application will be described in detail in the following specific embodiments.
附图说明Description of the drawings
附图是用来提供对本申请的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本申请，但并不构成对本申请的限制。在附图中：The accompanying drawings are used to provide a further understanding of the application and constitute a part of the specification. Together with the following specific implementations, they are used to explain the application, but do not constitute a limitation to the application. In the attached picture:
图1是根据本申请的一种实施方式的有机电致发光器件的结构示意图。Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present application.
图2是根据本申请的一种实施方式的电子装置的结构示意图。Fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
图中主要器件附图标记说明如下：The reference signs of the main components in the figure are explained as follows:
100、阳极；200、阴极；310、空穴注入层；321、空穴传输层；322、电子阻挡层；330、有机发光层；340、电子传输层；350、电子注入层；400、电子装置。100. Anode; 200. Cathode; 310. Hole injection layer; 321. Hole transport layer; 322. Electron blocking layer; 330. Organic light-emitting layer; 340. Electron transport layer; 350. Electron injection layer; 400. Electronic device .
具体实施方式Detailed ways
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。The specific implementation of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific implementations described here are only used to illustrate and explain the application, and are not used to limit the application.
在图中，为了清晰，可能夸大了区域和层的厚度。在图中相同的附图标记表示相同或类似的结构，因而将省略它们的详细描述。In the figure, the thickness of regions and layers may be exaggerated for clarity. The same reference numerals in the figures indicate the same or similar structures, and thus their detailed descriptions will be omitted.
在本申请中，
Figure PCTCN2020122273-appb-000002
和
Figure PCTCN2020122273-appb-000003
含义一样，均是指与其他取代基或结合位置结合的位置。 In this application,
Figure PCTCN2020122273-appb-000002
with
Figure PCTCN2020122273-appb-000003
They have the same meaning, and they all refer to the positions where they are combined with other substituents or bonding positions.
在本申请中，W的碳原子数，指的是所有碳原子数。举例而言，若W选自取代的碳原子数为40的芳基，则芳基及其上的取代基的所有碳原子数为40；若W为9,9-二甲基芴基，则其属于取代的碳原子数为15的芴基，W成环碳原子数为13。In this application, the number of carbon atoms of W refers to the number of all carbon atoms. For example, if W is selected from substituted aryl groups with 40 carbon atoms, all carbon atoms of the aryl group and the substituents thereon are 40; if W is 9,9-dimethylfluorenyl, then It belongs to the substituted fluorenyl group with 15 carbon atoms, and the ring carbon atom number of W is 13.
在本申请中，L和Ar中，取代的芳基或杂芳基的的碳原子数，指的是芳基或杂芳基及其上的取代基的碳原子总数，例如碳原子数为18的取代的芳基，指的是芳基和取代基的总碳原子数为18。例如2,4-二苯基-1,3,5-三嗪基就属于碳原子数为15的取代的杂芳基。In this application, the number of carbon atoms of a substituted aryl or heteroaryl group in L and Ar refers to the total number of carbon atoms of the aryl or heteroaryl group and its substituents, for example, the number of carbon atoms is 18. The substituted aryl group means that the total number of carbon atoms of the aryl group and the substituent is 18. For example, 2,4-diphenyl-1,3,5-triazinyl is a substituted heteroaryl group with 15 carbon atoms.
在本说明书中“碳原子数为6～40的取代或未取代的芳基”和“取代或未取代的碳原子数为6～40的芳基”两种表述含义相同，均是指芳基及其上的取代基的总碳原子数为6～40。同样的，在本说明书中“碳原子数为3～30的取代或未取代的杂芳基”和“取代或未取代的碳原子数为3～30的杂芳基”两种表述含义相同，均是指杂芳基及其上的取代基的总碳原子数为3～30。In this specification, "substituted or unsubstituted aryl group having 6 to 40 carbon atoms" and "substituted or unsubstituted aryl group having 6 to 40 carbon atoms" have the same meaning, and both refer to aryl groups. The total number of carbon atoms of the substituents thereon is 6-40. Similarly, in this specification, "substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms" and "substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms" have the same meaning. Both mean that the total number of carbon atoms of the heteroaryl group and the substituents thereon is 3-30.
在本说明书中“碳原子数为6～40的取代或未取代的芳基”和“取代或未取代的碳原子数为6～40的芳基”两种表述含义相同，均是指芳基及其上的取代基的总碳原子数为6～40。同样的，在本说明书中“碳原子数为3～30的取代或未取代的杂芳基”和“取代或未取代的碳原子数为3～30的杂芳基”两种表述含义相同，均是指杂芳基及其上的取代基的总碳原子数为3～30。In this specification, "substituted or unsubstituted aryl group having 6 to 40 carbon atoms" and "substituted or unsubstituted aryl group having 6 to 40 carbon atoms" have the same meaning, and both refer to aryl groups. The total number of carbon atoms of the substituents thereon is 6-40. Similarly, in this specification, "substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms" and "substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms" have the same meaning. Both mean that the total number of carbon atoms of the heteroaryl group and the substituents thereon is 3-30.
在本申请中，当没有另外提供具体的定义时，“杂”是指在一个官能团中包括至少1个B、N、O、S、Se、Si或P等杂原子且其余原子为碳和氢。未取代的烷基可以是没有任何双键或三键的“饱和烷基基团”。In this application, when no specific definition is provided otherwise, "hetero" means that a functional group includes at least one heteroatom such as B, N, O, S, Se, Si, or P, and the remaining atoms are carbon and hydrogen. . The unsubstituted alkyl group may be a "saturated alkyl group" without any double or triple bonds.
在本申请中所采用的描述方式“各……独立地为”与“……分别独立地为”和“……独立地选自”可以互换，均应做广义理解，其既可以是指在不同基团中，相同符号之间所表达的具体选项之间互相不影响，也可以表示在相同的基团中，相同符号之间所表达的具体选项之间互相不影响。举例而言：在“
Figure PCTCN2020122273-appb-000004
其中，各q独立地为0、1、2或3，各R”独立地选自氢、氟、氯”的描述中，其含义是：式Q-1表示苯环上有q个取代基R”，各个R”可以相同也可以不同，每个R”的选项之间互不影响；式Q-2表示联苯的每一个苯环上有q个取代基R”，两个苯环上的R”取代基的个数q可以相同或不同，各个R”可以相同也可以不同，每个R”的选项之间互不影响。 The description methods used in this application "each... are independently" and "... are independently" and "... are independently selected from" are interchangeable, and should be understood in a broad sense, which can mean either In different groups, the specific options expressed between the same symbols do not affect each other, or it can mean that the specific options expressed between the same symbols do not affect each other in the same group. For example: in "
Figure PCTCN2020122273-appb-000004
Wherein, each q is independently 0, 1, 2 or 3, and each R "independently selected from hydrogen, fluorine, and chlorine" in the description, its meaning is: formula Q-1 represents that there are q substituents R on the benzene ring ", each R" can be the same or different, and the options of each R" do not affect each other; formula Q-2 means that there are q substituents R" on each benzene ring of biphenyl, and the two benzene rings The number q of R" substituents may be the same or different, and each R" may be the same or different, and the options of each R" do not affect each other.
本申请中，“任选”或者“任选地”意味着随后所描述的事件或者环境可以发生也可以不发生，该说明包括该事情或者环境发生或者不发生的场合。例如，“任选被烷基取代的杂环基团”意味着烷基可以但不必须存在，该说明包括杂环基团被烷基取代的情景和杂环基团不被烷基取代的情景。“连接于同一原子上的两个取代基之间相互连接以与它们共同连接的原子形成饱和或不饱和的5～18元脂肪族环或5～18元芳香环”意味着连接于同一个原子上的两个取代基可以成环但不必须成环，包括二者相互连接成成饱和或不饱和的5～18元脂肪族环或5～18元芳香环的情景，也包括二者相互独立地存在的情景。In this application, "optional" or "optionally" means that the event or environment described later may or may not occur, and the description includes occasions where the event or environment occurs or does not occur. For example, "heterocyclic group optionally substituted by an alkyl group" means that an alkyl group may but does not have to be present, and the description includes the scenario where the heterocyclic group is substituted by an alkyl group and the scenario where the heterocyclic group is not substituted by an alkyl group. . "Two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5- to 18-membered aliphatic ring or 5- to 18-membered aromatic ring with the atoms they are commonly connected to" means that they are connected to the same atom The two substituents on the above can form a ring but do not have to form a ring, including the situation where the two are connected to form a saturated or unsaturated 5-18 membered aliphatic ring or a 5-18 membered aromatic ring, and also include the two independent of each other The scene of the existence of the earth.
在本申请中，术语“取代或未取代的”是指没有取代基或者被一个或多个取代基取代。所述取代基包括但不限于，氘、卤素基团(F、Cl、Br)、氰基、烷基、烯基、炔基、卤代烷基、芳基、杂芳基、芳氧基、芳硫基、烷胺基、环烷基、杂环基、三烷基硅基、烷基、环烷基、烷氧基、烷硫基。In this application, the term "substituted or unsubstituted" means that it has no substituents or is substituted by one or more substituents. The substituents include, but are not limited to, deuterium, halogen groups (F, Cl, Br), cyano, alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, aryloxy, arylsulfide Group, alkylamino group, cycloalkyl group, heterocyclic group, trialkylsilyl group, alkyl group, cycloalkyl group, alkoxy group, alkylthio group.
在本申请中，“烷基”可以包括直链烷基或支链烷基。烷基可具有1至12个碳原子，在本申请中，诸如“1至12”的数值范围是指给定范围中的各个整数；例如，“1至12个碳原子”是指可包含1个碳原子、2个碳原子、3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子、10个碳原子、11个碳原子、12个碳原子的烷基。烷基还可为具有1至10个碳原子的中等大小烷基。烷基还可为具有1至6个碳原子的低级烷基。在又一些实施方案中，烷基基团含有1-4个碳原子；还在一些实施方案中，烷基基团含有1-3个碳原子。所述烷基基团可以任选地被一个或多个本发明描述的取代基所取代。烷基基团的实例包含，但并不限于，甲基(Me、-CH 3)，乙基(Et、-CH 2CH 3)，正丙基(n-Pr、-CH 2CH 2CH 3)，异丙基(i-Pr、-CH(CH 3) 2)，正丁基(n-Bu、-CH 2CH 2CH 2CH 3)，异丁基(i-Bu、-CH 2CH(CH 3) 2)，仲丁基(s-Bu、-CH(CH 3)CH 2CH 3)，叔丁基(t-Bu、-C(CH 3) 3)等。此外，烷基可为取代的或未取代的。 In the present application, "alkyl" may include linear or branched alkyl. Alkyl groups can have 1 to 12 carbon atoms. In this application, a numerical range such as "1 to 12" refers to each integer in the given range; for example, "1 to 12 carbon atoms" means that it can contain 1 Carbon atoms, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 A carbon atom, 12 carbon atom alkyl group. The alkyl group may also be a medium-sized alkyl group having 1 to 10 carbon atoms. The alkyl group may also be a lower alkyl group having 1 to 6 carbon atoms. In still other embodiments, the alkyl group contains 1-4 carbon atoms; in still other embodiments, the alkyl group contains 1-3 carbon atoms. The alkyl group may be optionally substituted with one or more substituents described in the present invention. Examples of alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), isopropyl (i-Pr, -CH(CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH(CH 3 )CH 2 CH 3 ), tert-butyl (t-Bu, -C(CH 3 ) 3 ), etc. In addition, the alkyl group may be substituted or unsubstituted.
在本申请中，“烯基”是指在直链或支链烃链中包含一个或多个双键的烃基。烯基可为未取代的或取代的。烯基可具有2至12个碳原子，每当在本文出现时，诸如“2至12”的数值范围是指给定范围中的各个整数；例如，“2至20个碳原子”是指可包含2个碳原子、3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子、10个碳原子、11个碳原子、12个碳原子的烯基。例如，烯基可以为乙烯基、丁二烯、或1,3,5-己三烯。In this application, "alkenyl" refers to a hydrocarbon group containing one or more double bonds in a straight or branched hydrocarbon chain. Alkenyl groups can be unsubstituted or substituted. Alkenyl groups can have 2 to 12 carbon atoms, and whenever it appears herein, a numerical range such as "2 to 12" refers to each integer in the given range; for example, "2 to 20 carbon atoms" means that Contains 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms , Alkenyl of 12 carbon atoms. For example, the alkenyl group may be vinyl, butadiene, or 1,3,5-hexatriene.
在本申请中，环烷基指的是环状饱和烃，包含单环和多环结构。环烷基可具有3至12个碳原子，诸如“3至12”的数值范围是指给定范围中的各个整数；例如，“3至12个碳原子”是指可包含3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子、10个碳原子、11个碳原子、12个碳原子的环烷基。环烷基还可分为单环(只有一个环)、双环(两个环)或多环(三个或以上环)。环烷基还可分为两个环共用一个碳原子(螺环)、两个环共用两个碳原子(稠环)和两个环共用两个以上碳原子(桥环)。此外，环烷基可为取代的或未取代的。在一些实施方式中环烷基为5至10元环烷基，在另一些实施方式中，环烷基为5至8元环烷基，举例而言，环烷基的示例可以是，但不限于：五元环烷基即环戊基、六元环烷基即环己烷基、10元多环烷基如金刚烷基等。In this application, cycloalkyl refers to cyclic saturated hydrocarbons, including monocyclic and polycyclic structures. Cycloalkyl groups can have 3 to 12 carbon atoms, and a numerical range such as "3 to 12" refers to each integer in the given range; for example, "3 to 12 carbon atoms" means that it can contain 3 carbon atoms, Cycloalkyl groups of 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, and 12 carbon atoms. Cycloalkyl groups can also be classified as monocyclic (only one ring), bicyclic (two rings), or polycyclic (three or more rings). Cycloalkyl groups can also be divided into two rings sharing one carbon atom (spiro ring), two rings sharing two carbon atoms (fused ring), and two rings sharing two or more carbon atoms (bridged ring). In addition, cycloalkyl groups may be substituted or unsubstituted. In some embodiments, the cycloalkyl group is a 5- to 10-membered cycloalkyl group. In other embodiments, the cycloalkyl group is a 5- to 8-membered cycloalkyl group. For example, examples of the cycloalkyl group may be, but are not limited to : Five-membered cycloalkyl is cyclopentyl, six-membered cycloalkyl is cyclohexyl, 10-membered polycyclic alkyl such as adamantyl, etc.
本申请中，作为取代基的卤素基团，有氟、氯、溴或碘。In this application, the halogen group as the substituent includes fluorine, chlorine, bromine or iodine.
本申请中，“烷氧基”表示烷基基团通过氧原子与分子其余部分相连，其中烷基基团具有如本发明所述的含义。除非另外详细说明，所述烷氧基基团含有1～12个碳原子。在一实施方案中，烷氧基基团含有1～6个碳原子；在另一实施方案中，烷氧基基团含有1～4个碳原子；在又一实施方案中，烷氧基基团含有1～3个碳原子。所述烷氧基基团可以任选地被一个或多个本发明描述的取代基所取代。In the present application, "alkoxy" means that the alkyl group is connected to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described in the present invention. Unless otherwise specified, the alkoxy group contains 1-12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in another embodiment, the alkoxy group The group contains 1 to 3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents described in this invention.
烷氧基基团的实例包括，但并不限于，甲氧基(MeO、-OCH 3)，乙氧基(EtO、-OCH 2CH 3)，1-丙氧基(n-PrO、n-丙氧基、-OCH 2CH 2CH 3)，2-丙氧基(i-PrO、i-丙氧基、-OCH(CH 3) 2)，1-丁氧基(n-BuO、n-丁氧基、-OCH 2CH 2CH 2CH 3)，2-甲基-l-丙氧基(i-BuO、i-丁氧基、-OCH 2CH(CH 3) 2)，2-丁氧基(s-BuO、s-丁氧基、-OCH(CH 3)CH 2CH 3)，2-甲基-2-丙氧基(t-BuO、t-丁氧基、-OC(CH 3) 3)，等等。 Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH 3 ), ethoxy (EtO, -OCH 2 CH 3 ), 1-propoxy (n-PrO, n- Propoxy, -OCH 2 CH 2 CH 3 ), 2-propoxy (i-PrO, i-propoxy, -OCH(CH 3 ) 2 ), 1-butoxy (n-BuO, n- Butoxy, -OCH 2 CH 2 CH 2 CH 3 ), 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH 2 CH(CH 3 ) 2 ), 2-but Oxygen (s-BuO, s-butoxy, -OCH(CH 3 )CH 2 CH 3 ), 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC(CH 3 ) 3 ), etc.
本申请中，“卤代烷基”或“卤代烷氧基”表示烷基或烷氧基基团被一个或多个卤素原子所取代，其中烷基和烷氧基基团具有如本发明所述的含义，这样的实例包含，但并不限于，三氟甲基、三氟甲氧基等。In this application, "haloalkyl" or "haloalkoxy" means that an alkyl group or an alkoxy group is substituted by one or more halogen atoms, wherein the alkyl group and the alkoxy group have the meaning as described in the present invention Such examples include, but are not limited to, trifluoromethyl, trifluoromethoxy, and the like.
在本申请中，芳基指的是衍生自芳香碳环的任选官能团或取代基。芳基可以是单环芳基或多环芳基，换言之，芳基可以是单环芳基、稠环芳基、通过碳碳键共轭连接的两个或者更多个单环芳基、通过碳碳键共轭连接的单环芳基和稠环芳基、通过碳碳键共轭连接的两个或者更多个稠环芳基。即，通过碳碳键共轭连接的两个或者更多个芳香基团也可以视为本申请的芳基。其中，芳基中不含有B、N、O、S、P和Si等杂原子。举例而言，在本申请中，联苯基、三联苯基等为芳基。芳基的实例可以包括但不限于，苯基、萘基、芴基、蒽基、菲基、联苯基、三联苯基、四联苯基、五联苯基、苯并[9,10]菲基、芘基、苯并荧蒽基、
Figure PCTCN2020122273-appb-000005
基等。 In this application, an aryl group refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl group can be a monocyclic aryl group or a polycyclic aryl group. In other words, the aryl group can be a monocyclic aryl group, a condensed ring aryl group, two or more monocyclic aryl groups conjugated by a carbon-carbon bond, through A monocyclic aryl group and a fused ring aryl group conjugated by carbon-carbon bonds, and two or more fused ring aryl groups conjugated by a carbon-carbon bond. That is, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in the present application. Among them, the aryl group does not contain heteroatoms such as B, N, O, S, P, and Si. For example, in this application, biphenyl, terphenyl, etc. are aryl groups. Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, benzo[9,10] Phenanthryl, pyrenyl, benzofluoranthene,
Figure PCTCN2020122273-appb-000005
Base and so on.
在本申请中，取代的芳基可以是芳基中的一个或者两个以上氢原子被诸如氘原子、卤素基团、-CN、芳基、杂芳基、三烷基硅基、烷基、环烷基、烷氧基、烷硫基、卤代烷基、芳氧基、芳硫基、 硅烷基、烷胺基、芳基、杂环基等基团取代。杂芳基取代的芳基的具体实例包括但不限于，二苯并呋喃基取代的苯基、二苯并噻吩取代的苯基、吡啶取代的苯基等。应当理解地是，取代的芳基的碳原子数，指的是芳基和芳基上的取代基的碳原子总数，例如碳原子数为18的取代的芳基，指的是芳基及其取代基的总碳原子数为18。In the present application, the substituted aryl group may be one or more hydrogen atoms in the aryl group, such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, Cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, aryl, heterocyclic and other groups are substituted. Specific examples of heteroaryl-substituted aryl groups include, but are not limited to, dibenzofuranyl-substituted phenyl groups, dibenzothiophene-substituted phenyl groups, pyridine-substituted phenyl groups, and the like. It should be understood that the number of carbon atoms of a substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group. For example, a substituted aryl group with 18 carbon atoms refers to an aryl group and its The total number of carbon atoms of the substituent is 18.
在本申请中，作为芳基的芴基可以被取代，两个取代基可以彼此结合形成螺结构，具体施例包括但不限于以下结构：In this application, the fluorenyl group as an aryl group can be substituted, and two substituent groups can be combined with each other to form a spiro structure. Specific examples include but are not limited to the following structures:
Figure PCTCN2020122273-appb-000006
Figure PCTCN2020122273-appb-000006
在本申请中，杂芳基是指环中包含至少一个杂原子的一价芳香环或其衍生物，杂原子可以是B、O、N、P、Si和S中的至少一种。杂芳基可以是单环杂芳基或多环杂芳基，换言之，杂芳基可以是单个芳香环体系，也可以是通过碳碳键共轭连接的多个芳香环体系，且任一芳香环体系为一个芳香单环或者一个芳香稠环。本申请中的“杂芳基”可以包括1、2、3、4、5、6、7、8、9或10个任选自B、O、N、P、Si、Se和S的杂原子，碳原子数可以是3～40个，在一些实施例中杂芳基的碳原子数可以是3～30个，在另一些实施例中，杂芳基的碳原子数可以是3～20个，或3～18个，或3～12个，或12～18个。举例而言，杂芳基的碳原子数量还可以是3个、4个、5个、6个、7个、8个、9个、10个、11个、12个、18个、20个或40个，当然，碳原子数还可以是其他数量，在此不再一一列举。In this application, a heteroaryl group refers to a monovalent aromatic ring containing at least one heteroatom in the ring or a derivative thereof. The heteroatom may be at least one of B, O, N, P, Si, and S. The heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. In other words, the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated through carbon-carbon bonds, and any aromatic The ring system is an aromatic monocyclic ring or an aromatic fused ring. The "heteroaryl group" in this application may include 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 heteroatoms selected from B, O, N, P, Si, Se and S , The number of carbon atoms can be 3 to 40, in some embodiments, the number of carbon atoms of the heteroaryl group can be 3 to 30, in other embodiments, the number of carbon atoms of the heteroaryl group can be 3 to 20 , Or 3 to 18, or 3 to 12, or 12 to 18. For example, the number of carbon atoms of a heteroaryl group can also be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 18, 20 or 40. Of course, the number of carbon atoms can also be other numbers, so I won't list them all here.
示例地，杂芳基可以包括噻吩基、呋喃基、吡咯基、咪唑基、噻唑基、噁唑基、噁二唑基、三唑基、吡啶基、联吡啶基、嘧啶基、三嗪基、吖啶基、哒嗪基、吡嗪基、喹啉基、喹唑啉基、喹喔啉基、吩噁嗪基、酞嗪基、吡啶并嘧啶基、吡啶并吡嗪基、吡嗪并吡嗪基、异喹啉基、吲哚基、咔唑基、苯并噁唑基、苯并咪唑基、苯并噻唑基、苯并咔唑基、苯并噻吩基、二苯并噻吩基、噻吩并噻吩基、苯并呋喃基、菲咯啉基、异噁唑基、噻二唑基、苯并噻唑基、吩噻嗪基、硅芴基、二苯并呋喃基以及N-芳基咔唑基(如N-苯基咔唑基)、N-杂芳基咔唑基(如N-吡啶基咔唑基)、N-烷基咔唑基(如N-甲基咔唑基)等，而不限于此。其中，噻吩基、呋喃基、菲咯啉基等为单个芳香环体系类型的杂芳基，N-芳基咔唑基、N-杂芳基咔唑基为通过碳碳键共轭连接的多环体系类型的杂芳基。Exemplarily, heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, Acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazine Azinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thiophene Thienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silylfluorenyl, dibenzofuranyl and N-arylcarbazole Group (such as N-phenylcarbazolyl), N-heteroarylcarbazolyl (such as N-pyridylcarbazolyl), N-alkylcarbazolyl (such as N-methylcarbazolyl), etc., Not limited to this. Among them, thienyl, furanyl, phenanthrolinyl, etc. are heteroaryl groups of a single aromatic ring system type, and N-arylcarbazolyl and N-heteroarylcarbazolyl are multiple groups conjugated through carbon-carbon bonds. Heteroaryl group of ring system type.
在本申请中，取代的杂芳基可以是杂芳基中的一个或者两个以上氢原子被诸如氘原子、卤素基团、-CN、芳基、杂芳基、三烷基硅基、烷基、环烷基、烷氧基、烷硫基、卤代烷基、芳氧基、芳硫基、硅烷基、烷胺基、芳基、杂环基等基团取代。芳基取代的杂芳基的具体实例包括但不限于苯基取代的二苯并呋喃基、苯基取代的二苯并噻吩基、苯基取代的吡啶基等。应当理解地是，取代的杂芳基的碳原子数，指的是杂芳基和杂芳基上的取代基的碳原子总数。In this application, the substituted heteroaryl group may be one or more hydrogen atoms in the heteroaryl group, such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkane Group, cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, aryl, heterocyclic and other groups are substituted. Specific examples of aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, phenyl-substituted pyridyl, and the like. It should be understood that the number of carbon atoms of the substituted heteroaryl group refers to the total number of carbon atoms of the heteroaryl group and the substituents on the heteroaryl group.
本说明书中，“硅烷基”和“烷基硅烷基”含义一样，均是指
Figure PCTCN2020122273-appb-000007
其中，R G1、R G2、R G3分别独立地为烷基，烷基硅烷基的具体实例，包括但不限于，三甲基硅烷基、三乙基硅烷基、叔丁基二甲基硅烷基、丙基二甲基硅烷基。 In this specification, "silyl group" and "alkylsilyl group" have the same meaning and both refer to
Figure PCTCN2020122273-appb-000007
Wherein, R G1 , R G2 , and R G3 are each independently an alkyl group. Specific examples of the alkylsilyl group include, but are not limited to, trimethylsilyl group, triethylsilyl group, and tert-butyldimethylsilyl group. , Propyldimethylsilyl.
本申请中，芳基甲硅烷基是指
Figure PCTCN2020122273-appb-000008
其中，R G4、R G5、R G6分别独立地为芳基，芳基硅烷基的具体实例，包括但不限于，三苯基硅烷基、二苯基硅烷基、苯基硅烷基等，但并不限定于此。 In this application, arylsilyl refers to
Figure PCTCN2020122273-appb-000008
Wherein, R G4 , R G5 , and R G6 are each independently an aryl group. Specific examples of the arylsilyl group include, but are not limited to, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc., but not Not limited to this.
在本申请中，成环碳原子数为3～n的杂芳基指的是杂芳基中位于杂芳环上的碳原子数是3～n个，杂芳基上的取代基中的碳原子数不计算在内。In this application, a heteroaryl group with 3 to n ring carbon atoms means that the number of carbon atoms in the heteroaryl ring is 3 to n, and the carbon in the substituent on the heteroaryl group The number of atoms is not counted.
在本申请中，对芳基的解释可应用于亚芳基，对杂芳基的解释同样应用于亚杂芳基，对烷基的解释可应用于亚烷基，对环烷基的解释可应用于亚环烷基。In this application, the explanation of aryl can be applied to arylene, the explanation of heteroaryl can be applied to heteroarylene, the explanation of alkyl can be applied to alkylene, and the explanation of cycloalkyl can be Applied to cycloalkylene.
在本发明中，n个原子形成的环体系，即为n元环。例如，苯基为6元芳基。6-10元芳环就是指苯环、茚环和萘环等。In the present invention, the ring system formed by n atoms is an n-membered ring. For example, phenyl is a 6-membered aryl group. 6-10 membered aromatic ring refers to benzene ring, indene ring, naphthalene ring and so on.
本申请中的“环”包含饱和环、不饱和环；饱和环即环烷基、杂环烷基，不饱和环，即环烯基、杂环烯基、芳基和杂芳基。The "ring" in this application includes saturated rings and unsaturated rings; saturated rings are cycloalkyl, heterocycloalkyl, and unsaturated rings, namely cycloalkenyl, heterocycloalkenyl, aryl and heteroaryl.
本申请中的不定位连接键，是指从环体系中伸出的单键
Figure PCTCN2020122273-appb-000009
或
Figure PCTCN2020122273-appb-000010
其表示该连接键的一端可以连接该键所贯穿的环体系中的任意位置，另一端连接化合物分子其余部分。例如，下式(X)中所示的，式(X)所表示的萘基通过两个贯穿双环的不定位连接键与分子其他位置连接，其所表示的含义，包括如式(X-1)～式(X-10)所示出的任一可能的连接方式。 The non-positioned link in this application refers to the single bond extending from the ring system
Figure PCTCN2020122273-appb-000009
or
Figure PCTCN2020122273-appb-000010
It means that one end of the link can be connected to any position in the ring system that the bond penetrates, and the other end is connected to the rest of the compound molecule. For example, as shown in the following formula (X), the naphthyl group represented by the formula (X) is connected to other positions of the molecule through two non-positioned linkages running through the bicyclic ring. )~Any possible connection shown in formula (X-10).
Figure PCTCN2020122273-appb-000011
Figure PCTCN2020122273-appb-000011
例如，下式(X’)中所示的，式(X’)所表示的菲基通过一个从一侧苯环中间伸出的不定位连接键与分子其他位置连接，其所表示的含义，包括如式(X’-1)～式(X’-4)所示出的任一可能的连接方式。For example, as shown in the following formula (X'), the phenanthryl group represented by the formula (X') is connected to other positions of the molecule through a non-positional linkage extending from the middle of the benzene ring on one side. It includes any possible connection modes shown in formula (X'-1) to formula (X'-4).
Figure PCTCN2020122273-appb-000012
Figure PCTCN2020122273-appb-000012
本申请中的不定位取代基，指的是通过一个从环体系中央伸出的单键连接的取代基，其表示该取代基可以连接在该环体系中的任何可能位置。例如，下式(Y)中所示的，式(Y)所表示的取代基R基通过一个不定位连接键与喹啉环连接，其所表示的含义，包括如式(Y-1)～式(Y-7)所示出的任一可能的连接方式。The non-positional substituent in this application refers to a substituent connected by a single bond extending from the center of the ring system, which means that the substituent can be attached to any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R group represented by the formula (Y) is connected to the quinoline ring through a non-localized linkage, and its meaning includes the following formula (Y-1) to Any possible connection mode shown in formula (Y-7).
Figure PCTCN2020122273-appb-000013
Figure PCTCN2020122273-appb-000013
本申请提供一种含氮化合物，所述含氮化合物的结构式如化学式(1)所示：The present application provides a nitrogen-containing compound, the structural formula of the nitrogen-containing compound is shown in the chemical formula (1):
Figure PCTCN2020122273-appb-000014
Figure PCTCN2020122273-appb-000014
其中，环A为成环碳原子数为10～14的稠合芳环或成环碳原子数为8～12的稠合杂芳环，且所述环A不是咔唑环；Wherein, ring A is a fused aromatic ring with 10 to 14 carbon atoms or a fused heteroaromatic ring with 8 to 12 carbon atoms, and the ring A is not a carbazole ring;
环B为苯环、成环碳原子数为10～14的稠合芳环或成环碳原子数为8～12的稠合杂芳环；Ring B is a benzene ring, a fused aromatic ring with 10 to 14 carbon atoms, or a fused heteroaromatic ring with 8 to 12 carbon atoms;
环C为苯环或成环碳原子数为10～14的稠合芳环；Ring C is a benzene ring or a condensed aromatic ring with 10-14 carbon atoms;
R 1、R 2、R 3、R 4彼此相同或不同，且分别独立地选自氘、卤素基团、氰基、碳原子数为1～12的卤代烷基、碳原子数为1～12的烷基、碳原子数为2～10的烯基、碳原子数为2～10的炔基、碳原子数为3～12的环烷基、碳原子数为2～10的杂环烷基、碳原子数为1～12的烷氧基、碳原子数为1～12的烷硫基、碳原子数为3～12的三烷基硅基、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基、碳原子数为6～20的芳氧基、碳原子数为6～20的芳硫基、碳原子数为6～18的芳基甲硅烷基； R 1 , R 2 , R 3 , and R 4 are the same or different from each other and are each independently selected from deuterium, halogen group, cyano group, halogenated alkyl group having 1 to 12 carbon atoms, and one having 1 to 12 carbon atoms Alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, heterocycloalkyl groups having 2 to 10 carbon atoms, Alkoxy groups having 1 to 12 carbon atoms, alkylthio groups having 1 to 12 carbon atoms, trialkylsilyl groups having 3 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, carbon A heteroaryl group having 3 to 20 atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms;
n 1表示取代基R 1的个数，n 2表示取代基R 2的个数，n 3表示取代基R 3的个数，n 4表示取代基R 4的个数，n 1、n 2、n 3、n 4彼此相同或者不同，且分别独立地选自0、1、2、3或4； n 1 represents the number of substituents R 1 , n 2 represents the number of substituents R 2 , n 3 represents the number of substituents R 3 , n 4 represents the number of substituents R 4 , n 1 , n 2 , n 3 and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4;
当n 1大于1时，任意两个所述R 1相同或者不同，当n 2大于1时，任意两个所述R 2相同或者不同；当n 3大于1时，任意两个所述R 3相同或者不同；当n 4大于1时，任意两个所述R 4相同或者不同； When n 1 is greater than 1, any two of R 1 are the same or different; when n 2 is greater than 1, any two of R 2 are the same or different; when n 3 is greater than 1, any two of R 3 The same or different; when n 4 is greater than 1, any two of the R 4 are the same or different;
W选自碳原子数为6～40的取代或者未取代的芳基、碳原子数为3～40的取代或者未取代的杂芳基；W is selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms;
W中的取代基彼此相同或不同，各自独立地选自如下基团所组成的组：氘，卤素基团，氰基，碳原子数为1～12的烷基，碳原子数为1～12的卤代烷基，碳原子数为3～10的环烷基，碳原子数为2～10的杂环烷基，碳原子数为7～10的芳烷基，碳原子数为4～10的杂芳烷基，任选地被0、1、2或3个选自氘、氟、氯、溴、氰基、烷基的取代基所取代的碳原子数为6～30的芳基，任选地被0、1、2或3个选自氘、氟、氯、溴、氰基、烷基的取代基所取代的碳原子数为3～30的杂芳基，碳原子数为1～12的烷氧基，碳原子数为1～12的烷硫基，碳原子数为3～12的三烷基硅烷基，碳原子数为6～30的芳基甲硅烷基，碳原子数为6～20的芳氧基，碳原子数为6～20的芳硫基；The substituents in W are the same or different, and are independently selected from the group consisting of deuterium, halogen group, cyano group, alkyl group with 1-12 carbon atoms, and 1-12 carbon atoms. The halogenated alkyl group, the cycloalkyl group with 3 to 10 carbon atoms, the heterocycloalkyl group with 2 to 10 carbon atoms, the aralkyl group with 7 to 10 carbon atoms, the heterocyclic alkyl group with 4 to 10 carbon atoms Aralkyl, optionally substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl, aryl groups having 6 to 30 carbon atoms, optionally Heteroaryl groups having 3 to 30 carbon atoms and 1 to 12 carbon atoms substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl The alkoxy group, an alkylthio group having 1 to 12 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and 6 carbon atoms ～20 aryloxy group, arylthio group with 6 to 20 carbon atoms;
在所述W中，当同一原子上具有两个取代基时，任选地，连接于同一原子上的两个取代基之间相互连接以与它们共同连接的原子形成饱和或不饱和的5～18元脂肪族环或5～18元芳香环。In the W, when there are two substituents on the same atom, optionally, the two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5~ 18-membered aliphatic ring or 5-18-membered aromatic ring.
在本申请中，环A指的是
Figure PCTCN2020122273-appb-000015
环B指的是
Figure PCTCN2020122273-appb-000016
其中，环A独立地为稠合芳环、稠合杂芳环；环B独立地为苯环、稠合芳环、稠合杂芳环，例如，萘环、蒽环、菲环、喹啉环、异喹啉环等。其中，
Figure PCTCN2020122273-appb-000017
表示化学键。举例而言，在化合物
Figure PCTCN2020122273-appb-000018
中，环A为萘环，环A上的取代基R 1个数为0；环B为萘环，环B上的取代基R 2个数为0。可以理解的是，环B至少包括一个苯环结构，这使得本申请的含氮化合物至少包括一个咔唑结构。 In this application, ring A refers to
Figure PCTCN2020122273-appb-000015
Ring B refers to
Figure PCTCN2020122273-appb-000016
Among them, ring A is independently a fused aromatic ring or a fused heteroaromatic ring; ring B is independently a benzene ring, a fused aromatic ring, or a fused heteroaromatic ring, such as naphthalene ring, anthracene ring, phenanthrene ring, quinoline Ring, isoquinoline ring, etc. in,
Figure PCTCN2020122273-appb-000017
Represents a chemical bond. For example, in the compound
Figure PCTCN2020122273-appb-000018
Among them, ring A is a naphthalene ring, and the number of substituents R 1 on ring A is 0; ring B is a naphthalene ring, and the number of substituents R 2 on ring B is 0. It is understandable that ring B includes at least one benzene ring structure, which makes the nitrogen-containing compound of the present application include at least one carbazole structure.
本申请化合物中，作为含氮化合物核心中一部分的金刚烷螺合稠合芴基具有较强的刚性以及第一 三重态能级，化合物中与稠合芴基共轭连接的咔唑环具有较好的空穴传输能力，因此本申请的含氮化合物适合作为有机电致发光器件中的发光层主体材料。金刚烷基与芴基螺合，其可以通过超共轭效应而大幅增加大平面共轭结构的电子云密度，增强含氮化合物的空穴迁移率，有助于促进发光层中空穴和电子的传输平衡，改善有机电致发光器件的效率性能。不仅如此，含氮化合物空穴传输性能的提升，可以提高电子和空穴在有机发光层中的复合率，减少或者避免电子穿过有机发光层而向空穴传输层传输，进而可以有效地保护空穴传输层材料免受电子的冲击，提高有机电致发光器件的寿命。不仅如此，螺合于芴基上的金刚烷基具有大的空间体积和较强的刚性，因此其可以降低大平面共轭结构之间的相互作用力，减小分子间π-π堆叠，调节分子间的堆叠程度，进而使得含氮化合物在成膜时能够具有更为稳定的无定形态，改善含氮化合物的成膜性，进而进一步提高有机电致发光器件的寿命。In the compound of the present application, the adamantane spiro-fused fluorenyl group as a part of the core of the nitrogen-containing compound has strong rigidity and the first triplet energy level, and the carbazole ring conjugated to the fused fluorenyl group in the compound has With better hole transport ability, the nitrogen-containing compound of the present application is suitable as the host material of the light-emitting layer in an organic electroluminescent device. The adamantyl group and the fluorenyl group are spiro, which can greatly increase the electron cloud density of the large planar conjugated structure through the hyperconjugation effect, enhance the hole mobility of the nitrogen-containing compound, and help promote the exchange of holes and electrons in the light-emitting layer Transmission balance improves the efficiency performance of organic electroluminescent devices. Not only that, the improvement of the hole transport performance of nitrogen-containing compounds can increase the recombination rate of electrons and holes in the organic light-emitting layer, reduce or prevent electrons from passing through the organic light-emitting layer to the hole transport layer, thereby effectively protecting The hole transport layer material is protected from the impact of electrons, and the life of the organic electroluminescent device is improved. Not only that, the adamantyl group screwed on the fluorene group has a large space volume and strong rigidity, so it can reduce the interaction force between the large plane conjugated structure, reduce the intermolecular π-π stacking, and adjust The degree of intermolecular stacking in turn enables the nitrogen-containing compound to have a more stable amorphous state during film formation, improves the film-forming properties of the nitrogen-containing compound, and further increases the life of the organic electroluminescent device.
在本申请的一种可选的实施方式中，所述式(1)中环A为萘环、蒽环、菲环、二苯并呋喃环、二苯并噻吩环、噻蒽环、吩噁噻环、二苯并二噁英环、10H-吩噻嗪或10H-吩噁嗪；所述环B为苯环、萘环、喹啉环或异喹啉环；所述环C选自苯环、萘环、蒽环或菲环。In an optional embodiment of the present application, the ring A in the formula (1) is a naphthalene ring, an anthracene ring, a phenanthrene ring, a dibenzofuran ring, a dibenzothiophene ring, a thianthene ring, a phenoxathi Ring, dibenzodioxin ring, 10H-phenothiazine or 10H-phenoxazine; said ring B is benzene ring, naphthalene ring, quinoline ring or isoquinoline ring; said ring C is selected from benzene ring , Naphthalene ring, anthracene ring or phenanthrene ring.
由于该含氮化合物中环A为稠合芳香环结构，因此该含氮化合物的大平面共轭结构更大、刚性更强、电子云密度更高，这使得含氮化合物的空穴传输能力更强，进而可以提高电子和空穴在有机发光层中的复合率，减少或者避免电子穿过有机发光层而向空穴传输层传输，进而可以有效地保护空穴传输层材料免受电子的冲击，提高有机电致发光器件的寿命发光。Since the ring A in the nitrogen-containing compound is a condensed aromatic ring structure, the large-planar conjugated structure of the nitrogen-containing compound is larger, more rigid, and has a higher electron cloud density, which makes the nitrogen-containing compound more capable of transporting holes In turn, it can increase the recombination rate of electrons and holes in the organic light-emitting layer, reduce or prevent electrons from passing through the organic light-emitting layer to the hole transport layer, and can effectively protect the hole transport layer material from the impact of electrons. Improve the lifetime of the organic electroluminescence device to emit light.
在本申请的一种可选的实施方式中，所述式(1)中的
Figure PCTCN2020122273-appb-000019
选自以下结构： In an optional implementation manner of the present application, in the formula (1)
Figure PCTCN2020122273-appb-000019
Selected from the following structures:
Figure PCTCN2020122273-appb-000020
Figure PCTCN2020122273-appb-000020
在本申请的一种可选的实施方式中，所述式(1)中的
Figure PCTCN2020122273-appb-000021
选自以下结构： In an optional implementation manner of the present application, in the formula (1)
Figure PCTCN2020122273-appb-000021
Selected from the following structures:
Figure PCTCN2020122273-appb-000022
Figure PCTCN2020122273-appb-000022
在本申请中，R 1、R 2、R 3、R 4和W的碳原子数，指的是所有碳原子数。举例而言，若W选自取代的碳原子数为10的芳基，则芳基及其上的取代基的所有碳原子数为10。再举例而言，若W为对叔丁基苯基，则W为取代的碳原子数为10的苯基，W的成环碳原子数为6。 In this application, the number of carbon atoms of R 1 , R 2 , R 3 , R 4 and W refers to the number of all carbon atoms. For example, if W is selected from substituted aryl groups having 10 carbon atoms, all carbon atoms of the aryl group and the substituents thereon are 10. For another example, if W is a p-tert-butylphenyl group, then W is a substituted phenyl group having 10 carbon atoms, and W has 6 ring carbon atoms.
在本申请中，当没有另外提供具体的定义时，“杂”是指在一个官能团中包括至少1个B、N、O、S、Se、Si或P等杂原子且其余原子为碳和氢。未取代的烷基可以是没有任何双键或三键的“饱和烷基基团”。In this application, when no specific definition is provided otherwise, "hetero" means that a functional group includes at least one heteroatom such as B, N, O, S, Se, Si, or P, and the remaining atoms are carbon and hydrogen. . The unsubstituted alkyl group may be a "saturated alkyl group" without any double or triple bonds.
可以理解的是，取代的芳基的碳原子数，指的是芳基及其芳基上的取代基的总碳原子数。例如，取代的碳原子数为18的芳基，指的是芳基和芳基上的取代基的碳原子总数为18个。举例而言，9,9-二甲基芴基为碳原子数为15的取代的芳基。It can be understood that the number of carbon atoms of the substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group. For example, the substituted aryl group with 18 carbon atoms means that the total number of carbon atoms of the aryl group and the substituent on the aryl group is 18. For example, 9,9-dimethylfluorenyl is a substituted aryl group having 15 carbon atoms.
在一些实施方案中，本申请的含氮化合物的结构式如化学式(f-1)～(f-16)中的任意一种所示：In some embodiments, the structural formula of the nitrogen-containing compound of the present application is shown in any one of chemical formulas (f-1) to (f-16):
Figure PCTCN2020122273-appb-000023
Figure PCTCN2020122273-appb-000023
Figure PCTCN2020122273-appb-000024
Figure PCTCN2020122273-appb-000024
在本申请的一种可选的实施方式中，所述式(1)中的
Figure PCTCN2020122273-appb-000025
选自以下结构： In an optional implementation manner of the present application, in the formula (1)
Figure PCTCN2020122273-appb-000025
Selected from the following structures:
Figure PCTCN2020122273-appb-000026
Figure PCTCN2020122273-appb-000026
在一些实施方案中，所述含氮化合物的结构式如化学式(f-17)～(f-32)中的任意一种所示：In some embodiments, the structural formula of the nitrogen-containing compound is shown in any one of chemical formulas (f-17) to (f-32):
Figure PCTCN2020122273-appb-000027
Figure PCTCN2020122273-appb-000027
Figure PCTCN2020122273-appb-000028
Figure PCTCN2020122273-appb-000028
在本申请的一些具体实施方式中，W为
Figure PCTCN2020122273-appb-000029
其中，其中，L各自独立地选自单键、碳原子数3-30的取代或未取代的亚杂芳基、碳原子数为6-30的取代或未取代的亚芳基；Ar选自碳原子数为3-30的取代或未取代的杂芳基、碳原子数为6-30的取代或未取代的芳基； In some specific embodiments of this application, W is
Figure PCTCN2020122273-appb-000029
Wherein, L is each independently selected from a single bond, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Ar is selected from A substituted or unsubstituted heteroaryl group with 3-30 carbon atoms, a substituted or unsubstituted aryl group with 6-30 carbon atoms;
所述L和Ar上的取代基为一个或多个，Ar和L中的各取代基彼此相同或不同，且各自独立地选自氘、卤素基团、氰基、碳原子数为6～20的芳基、碳原子数为3～20的取代或未取代的杂芳基、碳原子数为1～12的卤代烷基、碳原子数为1～12的烷基、碳原子数为3～12的环烷基、碳原子数为1～12的烷氧基、碳原子数为1～12的烷硫基、碳原子数为3～12的三烷基硅基、碳原子数为6～20的芳氧基、碳原子数为6～20的芳硫基和碳原子数为6～18的芳基甲硅烷基；The substituents on L and Ar are one or more, and the substituents in Ar and L are the same or different from each other, and are each independently selected from deuterium, halogen group, cyano group, and the number of carbon atoms is 6-20 Aryl groups, substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms, haloalkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 12 carbon atoms, and 3 to 12 carbon atoms A cycloalkyl group, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a carbon number of 6 to 20 The aryloxy group, the arylthio group with 6 to 20 carbon atoms, and the arylsilyl group with 6 to 18 carbon atoms;
当同一原子上具有两个取代基时，任选地，连接于同一原子上的两个取代基之间能够相互连接以与它们共同连接的原子形成饱和或不饱和的5～13元脂肪族环或5～13元芳香环。更具体地，所述 碳原子数为3～20的取代或未取代的杂芳基中的取代是指被选自：氟、氘、氰基、三氟甲基、三甲基硅烷基、甲基、乙基、异丙基、叔丁基、三氟甲基、环戊烷基、环己烷基、苯基、萘基、吡啶基的取代基所取代。When there are two substituents on the same atom, optionally, the two substituents connected to the same atom can be connected to each other to form a saturated or unsaturated 5- to 13-membered aliphatic ring with the atoms connected to them. Or 5-13 membered aromatic ring. More specifically, the substitution in the substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms means being selected from: fluorine, deuterium, cyano, trifluoromethyl, trimethylsilyl, methyl Substituents of phenyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexane, phenyl, naphthyl, and pyridyl.
其中，当L上具有多个取代基时，L上的取代基之间可以相同或不同，其中，当Ar上具有多个取代基时，Ar上的取代基之间可以相同或不同。Wherein, when there are multiple substituents on L, the substituents on L may be the same or different, and when there are multiple substituents on Ar, the substituents on Ar may be the same or different.
本申请中，取代基为“多个”意思是多于1个，可以是2个、3个、4个、5个、6个、7个或8个。In this application, the term "plurality" means more than one substituent, and it can be 2, 3, 4, 5, 6, 7, or 8.
在本申请的一些实施方案中，L选自单键、碳原子为6～25的取代或未取代的亚芳基、碳原子数5～14的取代或未取代的亚杂芳基。L中的取代基各自独立地选自：氘、氟、氯、溴、氰基、碳原子数为1～4的烷基、碳原子数为1～4的卤代烷基、碳原子数为3～9的三烷基硅基、碳原子数为3～10的环烷基、碳原子数为6～15的芳基和碳原子数为3～12的杂芳基，且当同一原子上具有两个取代基时，任选地，连接于同一原子上的两个取代基之间能够相互连接以与它们共同连接的原子形成饱和或不饱和的5～13元脂肪族环或5～13元芳香环。In some embodiments of the present application, L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 14 carbon atoms. The substituents in L are each independently selected from the group consisting of deuterium, fluorine, chlorine, bromine, cyano, alkyl groups having 1 to 4 carbon atoms, haloalkyl groups having 1 to 4 carbon atoms, and 3 to 4 carbon atoms. The trialkylsilyl group of 9, the cycloalkyl group having 3 to 10 carbon atoms, the aryl group having 6 to 15 carbon atoms and the heteroaryl group having 3 to 12 carbon atoms, and when there are two on the same atom In the case of a substituent, optionally, two substituents connected to the same atom can be connected to each other to form a saturated or unsaturated 5- to 13-membered aliphatic ring or 5- to 13-membered aromatic ring.
在本申请的一些实施方案中，所述L选自单键、取代或未取代的亚苯基、取代或未取代的亚二联苯基、取代或未取代的亚三联苯基、取代或未取代的亚萘基、取代或未取代的9,9-二甲基芴亚基、取代或未取代的亚芴基、取代或未取代的9,9-二甲基-9H-9-硅杂芴亚基、取代或未取代的二苯并呋喃亚基、取代或未取代二苯并噻吩亚基、取代或未取代的亚喹啉基、取代或未取代的亚异喹啉基、取代或未取代的亚咔唑基、取代或未取代的亚菲基、取代或未取代的亚蒽基、取代或未取代的亚吡啶基、取代或未取代的螺二芴亚基、螺[环戊烷-1,9’-芴]亚基、螺[环己烷-1,9’-芴]亚基中的一种，或者为上述亚基中两者或三者通过单键连接所形成的亚基基团；L中的取代基彼此相同或不同，各自独立地选自氘、氟、氯、氰基、甲基、乙基、异丙基、正丙基、叔丁基、甲氧基、乙氧基、三氟甲基、三甲基硅基、苯基、氰基取代的苯基、氟取代的苯基、萘基、喹啉、异喹啉基、吡啶基、环戊烷基、环己烷基所组成的组。In some embodiments of the application, the L is selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted phenylene Substituted naphthylene, substituted or unsubstituted 9,9-dimethylfluorenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted 9,9-dimethyl-9H-9-silyl Fluorene subunits, substituted or unsubstituted dibenzofuran subunits, substituted or unsubstituted dibenzothiophene subunits, substituted or unsubstituted quinolinylene, substituted or unsubstituted isoquinolinylene, substituted or Unsubstituted carbazolylidene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene, substituted or unsubstituted pyridylene, substituted or unsubstituted spirobifluorenylene, spiro[cyclopenta One of alkane-1,9'-fluorene] subunit, spiro[cyclohexane-1,9'-fluorene] subunit, or two or three of the above subunits connected by a single bond Subunit group; the substituents in L are the same or different from each other, each independently selected from deuterium, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, n-propyl, tert-butyl, methoxy , Ethoxy, trifluoromethyl, trimethylsilyl, phenyl, cyano substituted phenyl, fluorine substituted phenyl, naphthyl, quinoline, isoquinolyl, pyridyl, cyclopentyl , Cyclohexane group.
可选地，L选自单键、或者选自化学式j-1至化学式j-13所示的基团所组成的组：Optionally, L is selected from a single bond or a group consisting of groups represented by chemical formula j-1 to chemical formula j-13:
Figure PCTCN2020122273-appb-000030
Figure PCTCN2020122273-appb-000030
Figure PCTCN2020122273-appb-000031
Figure PCTCN2020122273-appb-000031
其中，M 2选自单键或者
Figure PCTCN2020122273-appb-000032
Among them, M 2 is selected from a single bond or
Figure PCTCN2020122273-appb-000032
Q 1～Q 5各自独立地选自N或者C(J 5)，且Q 1～Q 5中至少一个选自N；当Q 1～Q 5中的两个或者两个以上选自C(J 5)时，任意两个J 5相同或者不相同； Q 1 to Q 5 are each independently selected from N or C(J 5 ), and at least one of Q 1 to Q 5 is selected from N; when two or more of Q 1 to Q 5 are selected from C(J 5 ), any two J 5 are the same or different;
Q 6～Q 13各自独立地选自N或者C(J 6)，且Q 6～Q 13中至少一个选自N；当Q 6～Q 13中的两个或者两个以上选自C(J 6)时，任意两个J 6相同或者不相同； Q 6 to Q 13 are each independently selected from N or C(J 6 ), and at least one of Q 6 to Q 13 is selected from N; when two or more of Q 6 to Q 13 are selected from C(J 6 ), any two J 6 are the same or different;
Q 14～Q 23各自独立地选自N、C或者C(J 7)，且Q 14～Q 23中至少一个选自N；当Q 14～Q 23中的两个或者两个以上选自C(J 7)时，任意两个J 7相同或者不相同； Q 14 to Q 23 are each independently selected from N, C or C (J 7 ), and at least one of Q 14 to Q 23 is selected from N; when two or more of Q 14 to Q 23 are selected from C (J 7 ), any two J 7s are the same or different;
Q 24～Q 33各自独立地选自N、C或者C(J 8)，且Q 24～Q 33中至少一个选自N；当Q 24～Q 33中的两个或者两个以上选自C(J 8)时，任意两个J 8相同或者不相同； Q 24 to Q 33 are each independently selected from N, C or C (J 8 ), and at least one of Q 24 to Q 33 is selected from N; when two or more of Q 24 to Q 33 are selected from C (J 8 ), any two J 8s are the same or different;
E 1～E 14、J 5～J 8分别独立地选自：氢、氘、卤素基团、氰基、碳原子数为3～20的杂芳基、碳原子数为6～20的芳基、碳原子数为3～9的三烷基硅基、碳原子数为8～12的芳基甲硅烷基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为2～10的杂环烷基、碳原子数为4～10的杂环烯基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基、碳原子数为6～18的芳氧基、碳原子数为6～18的芳硫基； E 1 to E 14 and J 5 to J 8 are each independently selected from: hydrogen, deuterium, halogen group, cyano group, heteroaryl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms , Trialkylsilyl groups with 3-9 carbon atoms, arylsilyl groups with 8-12 carbon atoms, alkyl groups with 1-10 carbon atoms, haloalkyl groups with 1-10 carbon atoms , C 3-10 cycloalkyl, C 2-10 heterocycloalkyl, C 4-10 heterocycloalkenyl, C 1-10 alkoxy , Alkylthio groups having 1 to 10 carbon atoms, aryloxy groups having 6 to 18 carbon atoms, and arylthio groups having 6 to 18 carbon atoms;
e 1～e 14以e r表示，E 1～E 14以E r表示，r为变量，表示1～14的任意整数，e r表示取代基E r的数量；当r选自1、2、3、4、5、6、9、13或14时，e r选自1、2、3或者4；当r选自7或11时，e r选自1、2、3、4、5或者6；当r为12时，e r选自1、2、3、4、5、6或者7；当r选自8或10时，e r选自1、2、3、4、5、6、7或者8；当e r大于1时，任意两个E r相同或者不相同； e 1 ~ e 14 expressed in E r, E 1 ~ E 14 to E represented by r, r is a variable, represents any integer of 1 to 14, E r E r represents the number of substituents; when r is selected from 1,2, When 3, 4, 5, 6, 9, 13, or 14, e r is selected from 1, 2, 3 or 4; when r is selected from 7 or 11, e r is selected from 1, 2, 3, 4, 5 or 6; when r is 12, e r is selected from 1, 2, 3, 4, 5, 6 or 7; when r is selected from 8 or 10, e r is selected from 1, 2, 3, 4, 5, 6 , 7 or 8; when e r is greater than 1, any two E r are the same or different;
K 3选自O、S、Se、N(E 15)、C(E 16E 17)、Si(E 18E 19)；其中，各E 15、E 16、E 17、E 18和E 19分别独立地选自：氢、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基； K 3 is selected from O, S, Se, N (E 15 ), C (E 16 E 17 ), Si (E 18 E 19 ); wherein each of E 15 , E 16 , E 17 , E 18 and E 19 are respectively Independently selected from: hydrogen, aryl groups having 6 to 20 carbon atoms, heteroaryl groups having 3 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and rings having 3 to 10 carbon atoms alkyl;
或者，任选地，上述E 16和E 17相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环； Or, optionally, the above-mentioned E 16 and E 17 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
或者，任选地，上述E 18和E 19相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环； Or, optionally, the above-mentioned E 18 and E 19 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
各K 4独立地选自单键、O、S、Se、N(E 20)、C(E 21E 22)、Si(E 23E 24)；其中，各E 20、E 21、E 22、E 23、E 24分别独立地选自：氢、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基、碳原子数为2～10的杂环烷基； Each K 4 is independently selected from a single bond, O, S, Se, N (E 20 ), C (E 21 E 22 ), Si (E 23 E 24 ); wherein, each of E 20 , E 21 , E 22 , E 23 and E 24 are each independently selected from: hydrogen, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and the number of carbon atoms It is a cycloalkyl group of 3-10, a heterocycloalkyl group of 2-10 carbon atoms;
或者，任选地，上述E 21和E 22相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环； Or, optionally, the above-mentioned E 21 and E 22 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
或者，任选地，上述E 23和E 24相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环。 Alternatively, optionally, the above-mentioned E 23 and E 24 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms with which they are commonly connected.
举例而言，L为
Figure PCTCN2020122273-appb-000033
时，当M 2和K 4为单键，E 11均为氢，K 3为C(E 16E 17)时，任选地，连接于同一个原子上的E 16和E 17相互连接以与它们共同连接的原子形成饱和或不饱和的5至13元脂肪族环指的是E 16和E 17可以相互连接形成一个5至13元环，也可以相互独立存在；当E 16和E 17形成脂肪族环时，该环的原子数可以是5元环，例如
Figure PCTCN2020122273-appb-000034
也可以是6元环，例如
Figure PCTCN2020122273-appb-000035
还可以是10元环，例如
Figure PCTCN2020122273-appb-000036
当然，E 16和E 17相互连接形成的环上的原子数还可以为其他数值，此处不再一一列举。同时，E 16和E 17相互连接形成的环还可以是芳香环，例如13元芳环，
Figure PCTCN2020122273-appb-000037
任选地，E 18和E 19相互连接以与它们共同连接的原子形成5到13元脂肪族环或芳香环的含义与E 16和E 17相同。任选地，E 21和E 22相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环的含义与E 16和E 17相同。任选地，E 23和E 24相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环的含义与E 16和E 17相同。 For example, L is
Figure PCTCN2020122273-appb-000033
When M 2 and K 4 are single bonds, E 11 are both hydrogen, and K 3 is C (E 16 E 17 ), optionally, E 16 and E 17 connected to the same atom are connected to each other with The atoms they connect together form a saturated or unsaturated 5- to 13-membered aliphatic ring means that E 16 and E 17 can be connected to each other to form a 5- to 13-membered ring, or they can exist independently of each other; when E 16 and E 17 form In the case of an aliphatic ring, the number of atoms of the ring can be a 5-membered ring, for example
Figure PCTCN2020122273-appb-000034
It can also be a 6-membered ring, for example
Figure PCTCN2020122273-appb-000035
It can also be a 10-membered ring, for example
Figure PCTCN2020122273-appb-000036
Of course, the number of atoms in the ring formed by the interconnection of E 16 and E 17 can also be other values, which will not be listed here. At the same time, the ring formed by the interconnection of E 16 and E 17 can also be an aromatic ring, such as a 13-membered aromatic ring,
Figure PCTCN2020122273-appb-000037
Optionally, E 18 and E 19 are connected to each other to form a 5- to 13-membered aliphatic ring or aromatic ring with the atoms they are commonly connected to have the same meaning as E 16 and E 17 . Optionally, E 21 and E 22 are connected to each other to form a 5- to 13-membered aliphatic ring or 5- to 13-membered aromatic ring with the atoms they are commonly connected to have the same meaning as E 16 and E 17 . Optionally, E 23 and E 24 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to have the same meaning as E 16 and E 17 .
可选地，Q 1～Q 5中只有一个选自N。 Optionally, only one of Q 1 to Q 5 is selected from N.
可选地，Q 6～Q 13中只有一个选自N。 Optionally, only one of Q 6 to Q 13 is selected from N.
可选地，Q 14～Q 23中只有一个选自N。 Optionally, only one of Q 14 to Q 23 is selected from N.
可选地，Q 24～Q 33中只有一个选自N。 Optionally, only one of Q 24 to Q 33 is selected from N.
在本申请的一些实施方案中，L选自单键、未取代的L 1、取代的L 1，其中，未取代的L 1选自如下基团所组成的组： In some embodiments of the present application, L is selected from the group consisting of a single bond, unsubstituted L 1 , and substituted L 1 , wherein the unsubstituted L 1 is selected from the group consisting of:
Figure PCTCN2020122273-appb-000038
Figure PCTCN2020122273-appb-000038
Figure PCTCN2020122273-appb-000039
Figure PCTCN2020122273-appb-000039
其中，取代的L 1为未取代的L 1被一个或者多个选自氘、氟、氯、溴、氰基、碳原子数为1～4的烷基、碳原子数为1～4的卤代烷基、碳原子数为3～9的三烷基硅基、碳原子数为3～10的环烷基、碳原子数为6～15的芳基和碳原子数为3～12的杂芳基所取代而形成的基团，且当取代的L 1上的取代基数量为多个时，任意两个取代基之间相同或者不同。进一步地，上述取代的L 1为未取代的L 1被0、1、2、3或4个选自氘、氟、氯、溴、氰基、甲基、乙基、丙基、叔丁基、苯基、联苯基、萘基、吡啶基、咔唑基、二苯并噻吩基、二苯并呋喃基的取代基所取代所形成的基团，且当取代的L 1上的取代基数量为多个时，任意两个取代基之间相同或者不同。 Wherein, the substituted L 1 is unsubstituted L 1 with one or more selected from deuterium, fluorine, chlorine, bromine, cyano, alkyl having 1 to 4 carbon atoms, and haloalkane having 1 to 4 carbon atoms Group, trialkylsilyl group with 3 to 9 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, aryl group with 6 to 15 carbon atoms, and heteroaryl group with 3 to 12 carbon atoms The group formed by substitution, and when the number of substituents on the substituted L 1 is more than one, any two substituents are the same or different. Further, the above-mentioned substituted L 1 is unsubstituted L 1 with 0, 1, 2, 3 or 4 selected from deuterium, fluorine, chlorine, bromine, cyano, methyl, ethyl, propyl, tert-butyl , Phenyl, biphenyl, naphthyl, pyridyl, carbazolyl, dibenzothienyl, and dibenzofuranyl substituents, and when the substituents on the substituted L 1 When the number is plural, any two substituents are the same or different.
在本申请的另一些更具体的实施方案中，所述L为单键或者如下基团中的任意一个：In other more specific embodiments of the present application, said L is a single bond or any one of the following groups:
Figure PCTCN2020122273-appb-000040
Figure PCTCN2020122273-appb-000040
Figure PCTCN2020122273-appb-000041
Figure PCTCN2020122273-appb-000041
在本申请的另一些更具体的实施方案中，所述L为单键或者如下基团中的任意一个：In other more specific embodiments of the present application, said L is a single bond or any one of the following groups:
Figure PCTCN2020122273-appb-000042
Figure PCTCN2020122273-appb-000042
在本申请的一些具体实施方式中，Ar选自化学式i-1至化学式i-18所示的基团所组成的组：In some specific embodiments of the present application, Ar is selected from the group consisting of groups represented by chemical formula i-1 to chemical formula i-18:
Figure PCTCN2020122273-appb-000043
Figure PCTCN2020122273-appb-000043
Figure PCTCN2020122273-appb-000044
Figure PCTCN2020122273-appb-000044
其中，M 1选自单键或者
Figure PCTCN2020122273-appb-000045
Among them, M 1 is selected from a single bond or
Figure PCTCN2020122273-appb-000045
G 1～G 5各自独立地选自N或者C(F 1)，且G 1～G 5中至少一个选自N；当G 1～G 5中的两个以上选自C(F 1)时，任意两个F 1相同或者不相同； G 1 to G 5 are each independently selected from N or C(F 1 ), and at least one of G 1 to G 5 is selected from N; when two or more of G 1 to G 5 are selected from C(F 1 ) , Any two F 1 are the same or different;
G 6～G 13各自独立地选自N或者C(F 2)，且G 6～G 13中至少一个选自N；当G 6～G 13中的两个以上选自C(F 2)时，任意两个F 2相同或者不相同； G 6 to G 13 are each independently selected from N or C(F 2 ), and at least one of G 6 to G 13 is selected from N; when two or more of G 6 to G 13 are selected from C(F 2 ) , Any two F 2 are the same or different;
G 14～G 23各自独立地选自N或者C(F 3)，且G 14～G 23中至少一个选自N；当G 14～G 23中的两个以上选自C(F 3)时，任意两个F 3相同或者不相同；或者，任选地，相邻的两个F 3相互连接形成5～10元芳环或5～10元杂芳环； G 14 to G 23 are each independently selected from N or C(F 3 ), and at least one of G 14 to G 23 is selected from N; when two or more of G 14 to G 23 are selected from C(F 3 ) , Any two F 3 are the same or different; or, optionally, two adjacent F 3 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring;
G 24～G 33各自独立地选自N或者C(F 4)，且G 24～G 33中至少一个选自N；当G 24～G 33中的两个以上选自C(F 4)时，任意两个F 4相同或者不相同；或者，任选地，相邻的两个F 4相互连接形成5～10元芳环或5～10元杂芳环； G 24 to G 33 are each independently selected from N or C(F 4 ), and at least one of G 24 to G 33 is selected from N; when two or more of G 24 to G 33 are selected from C(F 4 ) , Any two F 4 are the same or different; or, optionally, two adjacent F 4 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring;
G 34～G 37各自独立地选自N或者C(F 5)，当G 34～G 37中的两个以上选自C(F 5)时，任意两个F 5相同或者不相同；或者，任选地，相邻的两个F 5相互连接形成5～10元芳环或5～10元杂芳环； G 34 to G 37 are each independently selected from N or C(F 5 ), and when two or more of G 34 to G 37 are selected from C(F 5 ), any two F 5s are the same or different; or, Optionally, two adjacent F 5s are connected to each other to form a 5- to 10-membered aromatic ring or a 5- to 10-membered heteroaromatic ring;
G 38～G 45各自独立地选自N或者C(F 6)，且G 38～G 45中至少一个选自N；当G 38～G 45中的两个以上选自C(F 6)时，任意两个F 6相同或者不相同； G 38 to G 45 are each independently selected from N or C(F 6 ), and at least one of G 38 to G 45 is selected from N; when two or more of G 38 to G 45 are selected from C(F 6 ) , Any two F 6 are the same or different;
G 46～G 53各自独立地选自N或者C(F 7)，且G 46～G 53中至少一个选自N；当G 46～G 53中的两个或者两个以上选自C(F 7)时，任意两个F 7相同或者不相同；或者，任选地，相邻的两个F 7相互连接形成5～10元芳环或5～10元杂芳环。 G 46 to G 53 are each independently selected from N or C(F 7 ), and at least one of G 46 to G 53 is selected from N; when two or more of G 46 to G 53 are selected from C(F 7 ), any two F 7s are the same or different; or, optionally, two adjacent F 7s are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring.
式i-16中，“任选地，相邻的两个F 5相互连接形成5～10元芳环或5～10元杂芳环”意思是任意两个相邻的环原子，G 34和G 35、或者G 35和G 36、或者G 36和G 37，均为C(F 5)时，相邻的两个F 5可以相互独立地存在，也可以相互连接以与它们所连接的环原子一起形成一个稠合的芳环或杂芳环。举例而言，当i-16
Figure PCTCN2020122273-appb-000046
中，K 5为硫，G 34和G 35均为CH，G 36和G 37均为C(F 5)且二者形成6元芳环时，即式i-16为
Figure PCTCN2020122273-appb-000047
相邻的F 5成环还可以是形成其他的芳环或杂芳环，在此不再一一列举。任选地，相邻的两个F 3、F 4或F 7相互连接成环的含义与此相同，不再一一列举。 In formula i-16, "optionally, two adjacent F 5 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring" means any two adjacent ring atoms, G 34 and When G 35 , or G 35 and G 36 , or G 36 and G 37 , all are C (F 5 ), two adjacent F 5 can exist independently of each other, or they can be connected to each other to connect to the ring Together the atoms form a fused aromatic or heteroaromatic ring. For example, when i-16
Figure PCTCN2020122273-appb-000046
Where K 5 is sulfur, G 34 and G 35 are both CH, G 36 and G 37 are both C(F 5 ) and both form a 6-membered aromatic ring, that is, formula i-16 is
Figure PCTCN2020122273-appb-000047
The ring formation of adjacent F 5 can also be the formation of other aromatic or heteroaromatic rings, which will not be listed here. Optionally, two adjacent F 3 , F 4 or F 7 are connected to each other to form a ring with the same meaning, and will not be listed one by one.
D 1选自氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基； D 1 is selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and those having 1 to 10 carbon atoms A halogenated alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms;
D 2～D 9、D 21各自独立地选自：氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基、碳原子数为1～10的烷硫基、碳原子数为3～18的杂芳基； D 2 to D 9 and D 21 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl having 3 to 12 carbon atoms, and alkane having 1 to 10 carbon atoms Group, halogenated alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 10 carbon atoms, carbon Alkylthio groups having 1 to 10 atoms, heteroaryl groups having 3 to 18 carbon atoms;
D 10～D 20、F 1～F 7各自独立地选自：氢，氘，氟，氯，溴，氰基，碳原子数为3～12的三烷基硅基，碳原子数为1～10的烷基，碳原子数为1～10的卤代烷基，碳原子数为3～10的环烷基，碳原子数为1～10的烷氧基，碳原子数为1～10的烷硫基，任选地被0、1、2或3个选自氘、氟、氯、氰基、碳原子数为1～6的烷基、碳原子数为1～6的烷氧基、碳原子数为1～6的烷胺基、碳原子数为3～7的环烷基、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～4的烷氧基、碳原子数为1～4的卤代烷基、碳原子数为3～9的烷基硅烷基的取代基所取代的碳原子数为6～18的芳基、碳原子数为3～18的杂芳基； D 10 to D 20 and F 1 to F 7 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, and 1 to carbon atoms 10 alkyl groups, halogenated alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkyl sulfides with 1 to 10 carbon atoms Group, optionally with 0, 1, 2 or 3 selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, carbon atom Alkylamino group with 1 to 6, cycloalkyl with 3 to 7 carbon atoms, aryl with 6 to 15 carbon atoms, heteroaryl with 3 to 12 carbon atoms, 1 carbon atom ～4 alkoxy group, C 1-4 haloalkyl group, C 3-9 alkylsilyl group substituent substituted by C 6-18 aryl group, carbon number Heteroaryl groups of 3-18;
d 1～d 21以d k表示，D 1～D 21以D k表示，k为变量，表示1～21的任意整数，d k表示取代基D k的个数；其中，当k选自5或者17时，d k选自1、2或者3；当k选自2、7、8、12、15、16、18或者21时，d k选自1、2、3或者4；当k选自1、3、4、6、9或者14时，d k选自1、2、3、4或者5；当k为13时，d k选自1、2、3、4、5或者6；当k选自10或者19时，d k选自1、2、3、4、5、6或者7；当k为20时，d k选自1、2、3、4、5、6、7或者8；当k为11时，d k选自1、2、3、4、5、6、7、8或9；且当d k大于1时，任意两个D k相同或者不相同； d 1 ～d 21 are represented by d k , D 1 ～D 21 are represented by D k , k is a variable, representing any integer from 1 to 21, and d k is the number of substituents D k ; wherein, when k is selected from 5 Or when 17, d k is selected from 1, 2 or 3; when k is selected from 2, 7, 8, 12, 15, 16, 18 or 21, d k is selected from 1, 2, 3 or 4; when k is selected When from 1, 3, 4, 6, 9 or 14, d k is selected from 1, 2, 3, 4 or 5; when k is 13, d k is selected from 1, 2, 3, 4, 5 or 6; When k is selected from 10 or 19, d k is selected from 1, 2, 3, 4, 5, 6 or 7; when k is 20, d k is selected from 1, 2, 3, 4, 5, 6, 7 Or 8; when k is 11, d k is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; and when d k is greater than 1, any two D k are the same or different;
K 1和K 6分别独立地选自O、S、N(D 22)、C(D 23D 24)、Si(D 28D 29)；其中，各D 22、D 23、D 24、D 28、D 29分别独立地选自：碳原子数为6～18的芳基、碳原子数为3～18的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基； K 1 and K 6 are independently selected from O, S, N (D 22 ), C (D 23 D 24 ), Si (D 28 D 29 ); wherein, each of D 22 , D 23 , D 24 , D 28 , D 29 are independently selected from: aryl groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or 3 to 10 carbon atoms的cycloalkyl;
或者，任选地，上述D 23和D 24相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 23 and D 24 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
或者，任选地，上述D 28和D 29相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 28 and D 29 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
K 2选自单键、O、S、N(D 25)、C(D 26D 27)、Si(D 30D 31)；其中，各D 25、D 26、D 27、D 30、D 31分别独立地选自：碳原子数为6～18的芳基、碳原子数为3～18的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基， K 2 is selected from single bond, O, S, N (D 25 ), C (D 26 D 27 ), Si (D 30 D 31 ); wherein, each of D 25 , D 26 , D 27 , D 30 , D 31 They are independently selected from: aryl groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkanes having 3 to 10 carbon atoms base,
或者，任选地，上述D 26和D 27相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 26 and D 27 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
或者，任选地，上述D 30和D 31相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 30 and D 31 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
K 5选自O、S、Se、N(D 32)、C(D 33D 34)，其中，D 32、D 33和D 34各自独立地选自：碳原子数为6～18的芳基、碳原子数为3～18的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基。 K 5 is selected from O, S, Se, N(D 32 ), C(D 33 D 34 ), wherein D 32, D 33 and D 34 are each independently selected from: aryl groups having 6 to 18 carbon atoms , Heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 3 to 10 carbon atoms.
“任选地，上述D 23和D 24相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环”的意思是，D 23和D 24可以相互连接形成一个环，也可以相互独立存在。举例而言，在式i-19中，
Figure PCTCN2020122273-appb-000048
中，当M 1为单键，K 2为单键，D 19均为氢，K 1为C(D 23D 24)时，当D 23和D 24形成环时，该环可以是5元脂肪族环，例如
Figure PCTCN2020122273-appb-000049
也可以是6元脂肪族环，例如
Figure PCTCN2020122273-appb-000050
可以是13元芳香环，例如
Figure PCTCN2020122273-appb-000051
还可以是14元杂芳环，例如
Figure PCTCN2020122273-appb-000052
当然，D 23和D 24相互连接形成的环上的碳原子数还可以为其他数值，此处不再一一列举。任选地，D 26和D 27相互连接以与它们共同连接的原子形成5到14元脂肪族环或芳香环的涵义与D 23和D 24相同。任选地，D 28和D 29，D 26和D 27，D 30和D 31，相互连接以与它们共同连接的原子形成5到14元脂 肪族环或芳香环的涵义与D 23和D 24相同。 "Optionally, the above-mentioned D 23 and D 24 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms connected to them" means that D 23 and D 24 may be connected to each other to form one Rings can also exist independently of each other. For example, in formula i-19,
Figure PCTCN2020122273-appb-000048
In, when M 1 is a single bond, K 2 is a single bond, D 19 is both hydrogen, and K 1 is C (D 23 D 24 ), when D 23 and D 24 form a ring, the ring can be a 5-membered aliphatic Family ring, for example
Figure PCTCN2020122273-appb-000049
It can also be a 6-membered aliphatic ring, for example
Figure PCTCN2020122273-appb-000050
It can be a 13-membered aromatic ring, for example
Figure PCTCN2020122273-appb-000051
It can also be a 14-membered heteroaromatic ring, for example
Figure PCTCN2020122273-appb-000052
Of course, the number of carbon atoms in the ring formed by the interconnection of D 23 and D 24 can also be other values, which will not be listed here. Optionally, D 26 and D 27 are connected to each other to form a 5- to 14-membered aliphatic ring or aromatic ring with the atoms they are commonly connected to have the same meaning as D 23 and D 24. Optionally, D 28 and D 29 , D 26 and D 27 , D 30 and D 31 are connected to each other to form a 5- to 14-membered aliphatic or aromatic ring with the same meaning as D 23 and D 24 same.
可选地，G 1～G 5中至少两个选自N。 Optionally, at least two of G 1 to G 5 are selected from N.
可选地，G 6～G 13中至少两个选自N。 Optionally, at least two of G 6 to G 13 are selected from N.
可选地，G 14～G 23中至少两个选自N。 Optionally, at least two of G 14 to G 23 are selected from N.
可选地，G 24～G 33中至少两个选自N。 Optionally, at least two of G 24 to G 33 are selected from N.
可选地，G 38～G 45中至少两个选自N。 Optionally, at least two of G 38 to G 45 are selected from N.
可选地，G 46～G 53中至少两个选自N。 Optionally, at least two of G 46 to G 53 are selected from N.
在本申请的一些具体实施方式中，Ar选自碳原子数为6～25的取代或者未取代的芳基、碳原子数为3～25的取代或者未取代的杂芳基；Ar上的取代基为一个或多个，彼此相同或不同，且各自独立地选自氘、氟、氯、氰基、碳原子数为6～12的芳基、碳原子数为3～18的取代或未取代的杂芳基、碳原子数为1～6的烷基、碳原子数为1～6的卤代烷基、碳原子数为1～6的烷氧基、碳原子数为1～6的烷硫基、碳原子数为5～10的环烷基、碳原子数为3～9的三烷基硅基、碳原子数为6～20的芳氧基、碳原子数为6～20的芳硫基和碳原子数为6～18的芳基甲硅烷基。更具体地，所述碳原子数为3～18的取代或未取代的杂芳基中的取代是指被选自：氟、氘、氰基、三氟甲基、三甲基硅烷基、甲基、乙基、异丙基、叔丁基、三氟甲基、环戊烷基、环己烷基、苯基、萘基、吡啶基的取代基所取代。In some specific embodiments of the present application, Ar is selected from substituted or unsubstituted aryl groups with 6 to 25 carbon atoms, substituted or unsubstituted heteroaryl groups with 3 to 25 carbon atoms; substitution on Ar One or more groups, the same or different from each other, and each independently selected from deuterium, fluorine, chlorine, cyano, aryl groups with 6 to 12 carbon atoms, and substituted or unsubstituted with 3 to 18 carbon atoms Heteroaryl groups, alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms , Cycloalkyl groups with 5 to 10 carbon atoms, trialkylsilyl groups with 3 to 9 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, and arylthio groups with 6 to 20 carbon atoms And an arylsilyl group having 6 to 18 carbon atoms. More specifically, the substitution in the substituted or unsubstituted heteroaryl group having 3 to 18 carbon atoms means being selected from: fluorine, deuterium, cyano, trifluoromethyl, trimethylsilyl, methyl Substituents of phenyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, cyclopentyl, cyclohexane, phenyl, naphthyl, and pyridyl.
在本申请的一些更具体的实施方案中，Ar选自未取代的Ar 1或取代的Ar 1，其中，未取代的Ar 1选自如下基团所组成的组： In some more specific embodiments of the present application, Ar is selected from unsubstituted Ar 1 or substituted Ar 1 , wherein the unsubstituted Ar 1 is selected from the group consisting of the following groups:
Figure PCTCN2020122273-appb-000053
Figure PCTCN2020122273-appb-000053
Figure PCTCN2020122273-appb-000054
Figure PCTCN2020122273-appb-000054
其中，Z 1和Z 2各自独立地选自氢、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基；任意两个Z 1相同或者不相同，任意两个Z 2相同或者不相同； Wherein, Z 1 and Z 2 are each independently selected from hydrogen, an aryl group with 6 to 20 carbon atoms, and a heteroaryl group with 3 to 20 carbon atoms; any two Z 1s are the same or different, any two Z 2 is the same or different;
其中，取代的Ar 1为未取代的Ar 1被一个或者多个选自氘、氟、氯、氰基、碳原子数为1～4的烷基、碳原子数为1～4的烷氧基、碳原子数为1～4的烷胺基、碳原子数为3～7的环烷基、碳原子数为6～14的芳基、碳原子数为3～12的杂芳基、碳原子数为1～4的烷硫基、碳原子数为1～4的卤代烷基、碳原子数为3～9的烷基硅烷基所取代而形成的基团，且当Ar 1上的取代基的数量为多个时，任意两个取代基之间相同或者不相同。 Wherein, the substituted Ar 1 is unsubstituted Ar 1 with one or more selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 4 carbon atoms, and alkoxy with 1 to 4 carbon atoms. , Alkylamino groups with 1 to 4 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, heteroaryl groups with 3 to 12 carbon atoms, carbon atoms A group formed by the substitution of alkylthio groups having 1 to 4, haloalkyl groups having 1 to 4 carbon atoms, and alkylsilyl groups having 3 to 9 carbon atoms, and when the substituents on Ar 1 are When the number is more than one, any two substituents are the same or different.
需要说明的是，“取代的Ar 1”为未取代的Ar 1被一个或者多个取代基所取代，所述取代基可以替代上述未取代的Ar 1中的任意位置的氢原子，例如也可以是取代基团Z 1中的的任意氢原子。更进一步地，取代的Ar 1为未取代的Ar 1被一个或者多个选自氘、氟、氯、氰基、甲基、乙基、异丙基、叔丁基、甲氧基、乙氧基、异丙氧基、环戊基、环己基、苯基、萘基、吡啶基、三氟甲基、三甲基硅烷基所取代而形成的基团，且当Ar 1上的取代基的数量为多个时，任意两个取代基之间相同或者不相同。 It should be noted that “substituted Ar 1 ”means that the unsubstituted Ar 1 is substituted by one or more substituents, and the substituents can replace the hydrogen atom at any position in the unsubstituted Ar 1 described above, for example, Is any hydrogen atom in the substituent group Z 1. Furthermore, the substituted Ar 1 is unsubstituted Ar 1 with one or more selected from deuterium, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy Group, isopropoxy, cyclopentyl, cyclohexyl, phenyl, naphthyl, pyridyl, trifluoromethyl, trimethylsilyl, and when the substituent on Ar 1 is When the number is more than one, any two substituents are the same or different.
还在另一些具体的实施方案中，Ar选自未取代的Ar 1或取代的Ar 1，其中，未取代的Ar 1还选自如下基团所组成的组： In still other specific embodiments, Ar is selected from unsubstituted Ar 1 or substituted Ar 1 , wherein the unsubstituted Ar 1 is also selected from the group consisting of the following groups:
Figure PCTCN2020122273-appb-000055
其中，取代的Ar 1为未取代的Ar 1被一个或者多个选自氘、氟、氯、氰基、碳原子数为1～4的烷基、碳原子数为1～4的烷氧基、碳原子数为3～7的环烷基、碳原子数为6～14的芳基、碳原子数为3～12的杂芳基、碳原子数为1～4的烷硫基、碳原子数为1～4的卤代烷基、碳原子数为3～9 的烷基硅烷基所取代而形成的基团，且当Ar 1上的取代基的数量为多个时，任意两个取代基之间相同或者不相同。
Figure PCTCN2020122273-appb-000055
Wherein, the substituted Ar 1 is unsubstituted Ar 1 with one or more selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 4 carbon atoms, and alkoxy with 1 to 4 carbon atoms. , Cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, heteroaryl groups with 3 to 12 carbon atoms, alkylthio groups with 1 to 4 carbon atoms, carbon atoms A group formed by the substitution of a haloalkyl group having 1 to 4 and an alkylsilyl group having 3 to 9 carbon atoms, and when the number of substituents on Ar 1 is multiple, any two substituents Same or different between.
进一步地，Z 1和Z 2各自独立地选自：氢、取代或者未取代的苯基、取代或者未取代的萘基、取代或者未取代的蒽基、取代或者未取代的菲基、取代或者未取代的苝基、取代或者未取代的荧蒽基、取代或者未取代的
Figure PCTCN2020122273-appb-000056
基、取代或者未取代的联苯基、取代或者未取代的三联苯基、取代或者未取代的芴基、取代或者未取代的二苯并噻吩基、取代或者未取代的二苯并呋喃基、取代或者未取代的N-苯基咔唑基、取代或者未取代的咔唑-9-基苯基、取代或者未取代的吡啶基、取代或者未取代的嘧啶基、取代或者未取代的吡嗪基、取代或者未取代的喹啉基、取代或者未取代的异喹啉基、取代或者未取代的喹唑啉基、取代或者未取代的苯并噁嗪、取代或者未取代的三亚苯基； Further, Z 1 and Z 2 are each independently selected from: hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or Unsubstituted perylene, substituted or unsubstituted fluoranthene, substituted or unsubstituted
Figure PCTCN2020122273-appb-000056
Group, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, Substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted carbazol-9-ylphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazine Group, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted benzoxazine, substituted or unsubstituted triphenylene;
Z 1和Z 2中的取代基各自独立地选自：氟、氘、氰基、三氟甲基、三甲基硅烷基、甲基、乙基、异丙基、叔丁基、甲氧基、乙氧基、异丙氧基、三氟甲基、环戊烷基、环己烷基、苯基、萘基、吡啶基、嘧啶基、喹啉基、异喹啉基。需要说明的是，当Z 1或Z 2为氢时，不定位连接键也可以替代该氢原子连接在Ar 1上。例如，
Figure PCTCN2020122273-appb-000057
包含
Figure PCTCN2020122273-appb-000058
The substituents in Z 1 and Z 2 are each independently selected from: fluorine, deuterium, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy , Ethoxy, isopropoxy, trifluoromethyl, cyclopentyl, cyclohexane, phenyl, naphthyl, pyridyl, pyrimidinyl, quinolyl, isoquinolyl. It should be noted that when Z 1 or Z 2 is hydrogen, the hydrogen atom may be substituted for the hydrogen atom to be connected to Ar 1 without positioning the bonding bond. E.g,
Figure PCTCN2020122273-appb-000057
Include
Figure PCTCN2020122273-appb-000058
在本申请的一些实施例中，Ar可以选自芳基或富电子杂芳基，富电子杂芳基上杂原子在整体上能够增加杂芳基的共轭体系的电子云密度而不是降低杂芳基的共轭体系的电子云密度，例如杂原子上的孤对电子可以参与到共轭体系中而增加杂芳基的共轭体系的电子云密度。举例而言，富电子杂芳基可以包括但不限于咔唑基、二苯并呋喃基、二苯并噻唑基、呋喃基、吡咯基等。由于芳基和富电子杂芳基均能够有效地增强含氮化合物的电子云密度，并能够调整含氮化合物的HOMO能级，因此该含氮化合物将具有更佳地空穴传输能力。如此，该含氮化合物可以作为空穴型有机发光层主体材料，与用于传输电子的电子型有机发光层主体材料配合，共同形成有机发光层的主体材料。In some embodiments of the present application, Ar may be selected from aryl groups or electron-rich heteroaryl groups. The heteroatoms on the electron-rich heteroaryl groups can increase the electron cloud density of the conjugated system of the heteroaryl group as a whole instead of reducing the heteroaryl group. The electron cloud density of the conjugated system of the aryl group, for example, the lone pair of electrons on the heteroatom can participate in the conjugated system to increase the electron cloud density of the conjugated system of the heteroaryl group. For example, electron-rich heteroaryl groups may include, but are not limited to, carbazolyl, dibenzofuranyl, dibenzothiazolyl, furanyl, pyrrolyl, and the like. Since both the aryl group and the electron-rich heteroaryl group can effectively enhance the electron cloud density of the nitrogen-containing compound and can adjust the HOMO energy level of the nitrogen-containing compound, the nitrogen-containing compound will have better hole transport ability. In this way, the nitrogen-containing compound can be used as the host material of the hole-type organic light-emitting layer, and cooperate with the host material of the electron-type organic light-emitting layer for transporting electrons to form the host material of the organic light-emitting layer.
在本申请的一些实施例中，Ar选自以下结构：In some embodiments of the present application, Ar is selected from the following structures:
Figure PCTCN2020122273-appb-000059
Figure PCTCN2020122273-appb-000059
Figure PCTCN2020122273-appb-000060
Figure PCTCN2020122273-appb-000060
Figure PCTCN2020122273-appb-000061
Figure PCTCN2020122273-appb-000061
在本申请的一些实施例中，Ar为缺电子杂芳基(亦称贫电子杂芳基)，其上杂原子在整体上能够降低杂芳基的共轭体系的电子云密度而不是提高杂芳基的共轭体系的电子云密度，例如杂原子上的孤对电子不参与到共轭体系中，且杂原子由于较强的电负性而使得共轭体系的电子云密度降低。举例而言，缺电子杂芳基可以包括但不限于吡啶基、嘧啶基、均三嗪基、喹啉基、异喹啉基、苯并吡唑基、苯并咪唑基、喹喔啉基、菲啰啉基等。如此，Ar可以形成含氮化合物的电子传输核心基团，使得含氮化合物能够有效地实现电子传输，且能够有效的平衡电子和空穴在有机发光层的传输速率。如此，该含氮化合物既可以作为双极性有机发光层主体材料同时传输电子和空穴，也可以作为电子型有机发光层主体材料而与空穴型有机发光层主体材料配合。In some embodiments of the present application, Ar is an electron-deficient heteroaryl group (also known as an electron-poor heteroaryl group), on which heteroatoms can reduce the electron cloud density of the heteroaryl conjugate system as a whole instead of increasing the heteroaryl group. The electron cloud density of the conjugated system of the aryl group, for example, the lone pair of electrons on the heteroatom does not participate in the conjugated system, and the electron cloud density of the conjugated system is reduced due to the strong electronegativity of the heteroatom. For example, electron-deficient heteroaryl groups may include, but are not limited to, pyridinyl, pyrimidinyl, s-triazinyl, quinolinyl, isoquinolinyl, benzopyrazolyl, benzimidazolyl, quinoxalinyl, Phenanthroline and so on. In this way, Ar can form the electron transport core group of the nitrogen-containing compound, so that the nitrogen-containing compound can effectively realize electron transport, and can effectively balance the transmission rate of electrons and holes in the organic light-emitting layer. In this way, the nitrogen-containing compound can be used as the host material of the bipolar organic light-emitting layer to simultaneously transport electrons and holes, or can be used as the host material of the electron-type organic light-emitting layer to cooperate with the host material of the hole-type organic light-emitting layer.
在本申请的一些实施例中，Ar选自如下结构：In some embodiments of the present application, Ar is selected from the following structures:
Figure PCTCN2020122273-appb-000062
Figure PCTCN2020122273-appb-000062
Figure PCTCN2020122273-appb-000063
Figure PCTCN2020122273-appb-000063
在一些具体实施例中，R 1、R 2、R 3、R 4彼此相同或不同，且分别独立地选自氘、卤素基团、氰基、碳原子数为1～4的卤代烷基、碳原子数为1～4的烷基、碳原子数为2～6的烯基、碳原子数为2～6的炔基、碳原子数为5～10的环烷基、碳原子数为4～6的杂环烷基、碳原子数为1～4的烷氧基、碳原子数为1～4的烷硫基、碳原子数为3～9的三烷基硅基、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为6～15的芳氧基、碳原子数为6～15的芳硫基、三苯基甲硅烷基。 In some specific embodiments, R 1 , R 2 , R 3 , and R 4 are the same or different from each other, and are each independently selected from deuterium, halogen group, cyano group, halogenated alkyl group having 1 to 4 carbon atoms, carbon Alkyl groups having 1 to 4 atoms, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, 4 to carbon atoms 6 heterocycloalkyl groups, alkoxy groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms, trialkylsilyl groups having 3 to 9 carbon atoms, 6 carbon atoms -15 aryl groups, heteroaryl groups having 3 to 12 carbon atoms, aryloxy groups having 6 to 15 carbon atoms, arylthio groups having 6 to 15 carbon atoms, and triphenylsilyl groups.
在一些更具体实施例中，R 1、R 2、R 3、R 4彼此相同或不同，且分别独立地选自氘、氟、氯、溴、氰基、甲基、异丙基、乙基异丙基、环丙基、叔丁基、乙氧基、三氟甲基、三甲基硅烷基、苯基、吡啶基、二甲基芴基、二苯并呋喃基、二苯并噻吩基、嘧啶基、三嗪基、三苯基甲硅烷基，n 1、n 2、n 3、n 4彼此相同或者不同，且分别独立地选自0、1、2、3或4。 In some more specific embodiments, R 1 , R 2 , R 3 , R 4 are the same or different from each other, and are each independently selected from deuterium, fluorine, chlorine, bromine, cyano, methyl, isopropyl, ethyl Isopropyl, cyclopropyl, tert-butyl, ethoxy, trifluoromethyl, trimethylsilyl, phenyl, pyridyl, dimethylfluorenyl, dibenzofuranyl, dibenzothienyl , Pyrimidinyl, triazinyl, triphenylsilyl, n 1 , n 2 , n 3 , and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4, respectively.
可选地，所述含氮化合物选自如下化合物所组成的组：Optionally, the nitrogen-containing compound is selected from the group consisting of the following compounds:
Figure PCTCN2020122273-appb-000064
Figure PCTCN2020122273-appb-000064
Figure PCTCN2020122273-appb-000065
Figure PCTCN2020122273-appb-000065
Figure PCTCN2020122273-appb-000066
Figure PCTCN2020122273-appb-000066
Figure PCTCN2020122273-appb-000067
Figure PCTCN2020122273-appb-000067
Figure PCTCN2020122273-appb-000068
Figure PCTCN2020122273-appb-000068
Figure PCTCN2020122273-appb-000069
Figure PCTCN2020122273-appb-000069
Figure PCTCN2020122273-appb-000070
Figure PCTCN2020122273-appb-000070
本申请还提供一种有机电致发光器件，有机电致发光器件包括相对设置的阳极和阴极，以及设置于所述阳极和所述阴极之间的功能层，所述功能层包括空穴注入层、空穴传输层、有机发光层、电子传输层以及电子注入层；所述有机发光层包含上述的含氮化合物，以改善有机电致发光器件的电压特性、效率特性和寿命特性。The present application also provides an organic electroluminescent device. The organic electroluminescent device includes an anode and a cathode disposed oppositely, and a functional layer disposed between the anode and the cathode, and the functional layer includes a hole injection layer , Hole transport layer, organic light emitting layer, electron transport layer and electron injection layer; the organic light emitting layer contains the above-mentioned nitrogen-containing compound to improve the voltage characteristics, efficiency characteristics and life characteristics of the organic electroluminescent device.
举例而言，如图1所示，有机电致发光器件可以包括依次层叠设置的阳极100、空穴传输层 321、有机发光层330、电子传输层340和阴极200。本申请提供的含氮化合物可以应用于有机电致发光器件的有机发光层330，以提高有机电致发光器件的寿命、提高有机电致发光器件的发光效率或者降低有机电致发光器件的驱动电压。For example, as shown in FIG. 1, an organic electroluminescent device may include an anode 100, a hole transport layer 321, an organic light emitting layer 330, an electron transport layer 340, and a cathode 200 which are sequentially stacked. The nitrogen-containing compound provided in this application can be applied to the organic light-emitting layer 330 of an organic electroluminescent device to increase the life of the organic electroluminescent device, increase the luminous efficiency of the organic electroluminescent device, or reduce the driving voltage of the organic electroluminescent device .
可选地，阳极100包括阳极材料，其可选地为有助于空穴注入至功能层中的具有大逸出功(功函数，work function)的材料。阳极材料的具体实例包括但不限于：金属如镍、铂、钒、铬、铜、锌和金或它们的合金；金属氧化物如氧化锌、氧化铟、氧化铟锡(ITO)和氧化铟锌(IZO)；组合的金属和氧化物如ZnO:Al或SnO 2:Sb；或导电聚合物如聚(3-甲基噻吩)、聚[3,4-(亚乙基-1,2-二氧基)噻吩](PEDT)、聚吡咯和聚苯胺。可选包括包含氧化铟锡(铟锡氧化物，indium tin oxide)(ITO)作为阳极的透明电极。 Optionally, the anode 100 includes an anode material, which is optionally a material with a large work function (work function) that facilitates injection of holes into the functional layer. Specific examples of anode materials include, but are not limited to: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combined metals and oxides such as ZnO: Al or SnO 2 : Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-di (Oxy)thiophene] (PEDT), polypyrrole and polyaniline. Optionally, a transparent electrode containing indium tin oxide (ITO) as the anode is included.
可选地，空穴传输层321可以包括一种或者多种空穴传输材料，空穴传输材料可以选自咔唑多聚体、咔唑连接三芳胺类化合物或者其他类型的化合物，本申请对此不做特殊的限定。Optionally, the hole transport layer 321 may include one or more hole transport materials, and the hole transport materials may be selected from carbazole polymers, carbazole-linked triarylamine compounds or other types of compounds. This does not make special restrictions.
可选地，有机发光层330可以包括主体材料和客体材料，注入有机发光层330的空穴和注入有机发光层330的电子可以在有机发光层330复合而形成激子，激子将能量传递给主体材料，主体材料将能量传递给客体材料，进而使得客体材料能够发光。Optionally, the organic light-emitting layer 330 may include a host material and a guest material. The holes injected into the organic light-emitting layer 330 and the electrons injected into the organic light-emitting layer 330 can recombine in the organic light-emitting layer 330 to form excitons, and the excitons transfer energy to The host material, the host material transfers energy to the guest material, so that the guest material can emit light.
在本申请的一种实施方式中，主体材料可以由本申请的含氮化合物组成，尤其是由W基团中包括有缺电子芳杂环的含氮化合物组成。该类含氮化合物能够同时传输电子和空穴，且能够平衡空穴和电子的传输效率，因此电子和空穴能够在有机发光层内高效复合，提高有机电致发光器件的发光效率。In one embodiment of the present application, the host material may be composed of the nitrogen-containing compound of the present application, especially a nitrogen-containing compound containing an electron-deficient aromatic heterocycle in the W group. Such nitrogen-containing compounds can transport electrons and holes at the same time, and can balance the transmission efficiency of holes and electrons. Therefore, electrons and holes can be efficiently recombined in the organic light-emitting layer to improve the light-emitting efficiency of the organic electroluminescent device.
在本申请的另一种实施方式中，主体材料可以为复合材料，例如可以包括本申请的含氮化合物和电子型有机发光层主体材料。本申请的含氮化合物能够有效的传输空穴，使得空穴传输效率与有机发光层的电子传输效率相平衡，进而使得电子和空穴能够在有机发光层内高效复合，提高有机电致发光器件的发光效率。举例而言，主体材料可以包括本申请的含氮化合物和GH-n1。In another embodiment of the present application, the host material may be a composite material, for example, may include the nitrogen-containing compound of the present application and the host material of the electronic organic light-emitting layer. The nitrogen-containing compound of the present application can effectively transport holes, so that the hole transport efficiency is balanced with the electron transport efficiency of the organic light-emitting layer, so that electrons and holes can be efficiently recombined in the organic light-emitting layer, and the organic electroluminescent device is improved The luminous efficiency. For example, the host material may include the nitrogen-containing compound of the present application and GH-n1.
有机发光层330的客体材料可以为具有稠合芳基的化合物或其衍生物、具有杂芳基的化合物或其衍生物、芳香族胺衍生物或者其他材料，本申请对此不做特殊的限制。在本申请的一种实施方式中，有机发光层330的客体材料可以为Ir(piq) 2(acac)等。在本申请的另一种实施方式中，有机发光层330的客体材料可以为Ir(ppy) 3等。 The guest material of the organic light-emitting layer 330 may be a compound with a condensed aryl group or its derivative, a compound with a heteroaryl group or its derivative, an aromatic amine derivative, or other materials, which are not particularly limited in this application. . In an embodiment of the present application, the guest material of the organic light-emitting layer 330 may be Ir(piq) 2 (acac) or the like. In another embodiment of the present application, the guest material of the organic light-emitting layer 330 may be Ir(ppy) 3 or the like.
可选地，电子传输层340可以为单层结构，也可以为多层结构，其可以包括一种或者多种电子传输材料，电子传输材料可以选自但不限于，苯并咪唑衍生物、恶二唑衍生物、喹喔啉衍生物或者其他电子传输材料。Optionally, the electron transport layer 340 can be a single-layer structure or a multi-layer structure, which can include one or more electron transport materials, which can be selected from, but not limited to, benzimidazole derivatives, oxacin Diazole derivatives, quinoxaline derivatives or other electron transport materials.
可选地，阴极200可以包括阴极材料，其是有助于电子注入至功能层中的具有小逸出功的材料。阴极材料的具体实例包括但不限于，金属如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡和铅或它们的合金；或多层材料如LiF/Al、Liq/Al、LiO 2/Al、LiF/Ca、LiF/Al和BaF 2/Ca。可选包括包含铝的金属电极作为阴极。在本申请的一种实施方式中，阴极200的材料可以为镁银合金。 Optionally, the cathode 200 may include a cathode material, which is a material with a small work function that facilitates injection of electrons into the functional layer. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or their alloys; or multilayer materials such as LiF/Al , Liq/Al, LiO 2 /Al, LiF/Ca, LiF/Al and BaF 2 /Ca. Optionally, a metal electrode containing aluminum is included as a cathode. In an embodiment of the present application, the material of the cathode 200 may be a magnesium-silver alloy.
可选地，如图1所示，在阳极100和空穴传输层321之间还可以设置有空穴注入层310，以增强向第一空穴传输层321注入空穴的能力。空穴注入层310可以选用联苯胺衍生物、星爆状芳基胺类化合物、酞菁衍生物或者其他材料，本申请对此不做特殊的限制。例如，空穴注入层310可以由F4-TCNQ组成。Optionally, as shown in FIG. 1, a hole injection layer 310 may be further provided between the anode 100 and the hole transport layer 321 to enhance the ability of injecting holes into the first hole transport layer 321. The hole injection layer 310 can be selected from benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives or other materials, which are not particularly limited in this application. For example, the hole injection layer 310 may be composed of F4-TCNQ.
可选地，如图1所示，空穴传输层321和有机发光层330之间还可以设置有电子阻挡层322，以阻挡电子向空穴传输层321侧传输，提高电子和空穴在有机发光层330的复合率并保护空穴传输层321免受电子的冲击。电子阻挡层322的材料可以为咔唑多聚体、咔唑连接三芳胺类化合物或者其他可行的结构。Optionally, as shown in FIG. 1, an electron blocking layer 322 may be further provided between the hole transport layer 321 and the organic light-emitting layer 330 to block electrons from being transported to the hole transport layer 321 side, and improve electrons and holes in the organic The recombination rate of the light-emitting layer 330 protects the hole transport layer 321 from the impact of electrons. The material of the electron blocking layer 322 may be a carbazole polymer, a carbazole-linked triarylamine compound, or other feasible structures.
可选地，如图1所示，在阴极200和电子传输层340之间还可以设置有电子注入层350，以增强向电子传输层340注入电子的能力。电子注入层350可以包括有碱金属硫化物、碱金属卤化物等无机材料，或者可以包括碱金属与有机物的络合物。例如，电子注入层350可以包括LiQ。Optionally, as shown in FIG. 1, an electron injection layer 350 may be further provided between the cathode 200 and the electron transport layer 340 to enhance the ability to inject electrons into the electron transport layer 340. The electron injection layer 350 may include inorganic materials such as alkali metal sulfides and alkali metal halides, or may include complexes of alkali metals and organic substances. For example, the electron injection layer 350 may include LiQ.
本申请还提供一种电子装置400，如图2所示，该电子装置400包括上述有机电致发光器件实施 方式所描述的任意一种有机电致发光器件。该电子装置400可以为显示装置、照明装置、光通讯装置或者其他类型的电子装置，例如可以包括但不限于电脑屏幕、手机屏幕、电视机、电子纸、应急照明灯、光模块等。由于该电子装置400具有上述有机电致发光器件实施方式所描述的任意一种有机电致发光器件，因此具有相同的有益效果，本申请在此不再赘述。The present application also provides an electronic device 400. As shown in FIG. 2, the electronic device 400 includes any of the organic electroluminescent devices described in the foregoing organic electroluminescent device embodiments. The electronic device 400 may be a display device, a lighting device, an optical communication device or other types of electronic devices, such as but not limited to computer screens, mobile phone screens, televisions, electronic paper, emergency lighting, light modules, etc. Since the electronic device 400 has any one of the organic electroluminescent devices described in the foregoing organic electroluminescent device embodiments, it has the same beneficial effects, which will not be repeated here in this application.
合成例：Synthesis example:
下面所描述的合成例中，除非另有声明，否则所有的温度的单位为摄氏度。部分试剂购买于商品供应商如Aldrich Chemical Company,Arco Chemical Company and Alfa ChemicalCompany，除非另有声明，否则使用时都没有经过进一步纯化。其余的常规试剂从汕头西陇化工厂、广东光华化学试剂厂、广州化学试剂厂、天津好寓宇化学品有限公司、天津市福晨化学试剂厂、武汉鑫华远科技发展有限公司、青岛腾龙化学试剂有限公司和青岛海洋化工厂等处购买得到。无水四氢呋喃、二氧六环、甲苯、乙醚等无水溶剂是经过金属钠回流干燥得到。无水二氯甲烷和氯仿是经过氢化钙回流干燥得到。乙酸乙酯、石油醚、正己烷、N,N-二甲基乙酰胺和N,N-二甲基甲酰胺是经无水硫酸钠事先干燥后使用。In the synthesis examples described below, unless otherwise stated, all temperatures are in degrees Celsius. Some reagents are purchased from commodity suppliers such as Aldrich Chemical Company, Arco Chemical Company and Alfa Chemical Company. Unless otherwise stated, they are used without further purification. The remaining conventional reagents are from Shantou Xilong Chemical Factory, Guangdong Guanghua Chemical Reagent Factory, Guangzhou Chemical Reagent Factory, Tianjin Haoyuyu Chemical Co., Ltd., Tianjin Fuchen Chemical Reagent Factory, Wuhan Xinhuayuan Technology Development Co., Ltd., Qingdao Tenglong Purchased from Chemical Reagent Co., Ltd. and Qingdao Ocean Chemical Plant. Anhydrous tetrahydrofuran, dioxane, toluene, ether and other anhydrous solvents are obtained by refluxing and drying of sodium metal. Anhydrous dichloromethane and chloroform are obtained by refluxing and drying with calcium hydride. Ethyl acetate, petroleum ether, n-hexane, N,N-dimethylacetamide and N,N-dimethylformamide are used after being dried in advance with anhydrous sodium sulfate.
各合成例中的反应一般是在氮气或氩气正压下进行的，或者在无水溶剂上套一干燥管(除非另有声明)；在反应中，反应瓶都塞上合适的橡皮塞，底物通过注射器注入反应瓶中。所用到的各个玻璃器皿都是干燥过的。The reaction in each synthesis example is generally carried out under a positive pressure of nitrogen or argon, or a drying tube is placed on an anhydrous solvent (unless otherwise stated); during the reaction, the reaction flask is plugged with a suitable rubber stopper, The substrate is injected into the reaction flask via a syringe. All glassware used is dried.
在纯化时，色谱柱是硅胶柱，硅胶(300-400目)购于青岛海洋化工厂。In the purification, the chromatographic column was a silica gel column, and silica gel (300-400 mesh) was purchased from Qingdao Ocean Chemical Factory.
在各个合成例中，低分辨率质谱(MS)数据的测定条件是：Agilent 6120四级杆HPLC-M(柱子型号：Zorbax SB-C18,2.1×30mm,3.5微米,6min,流速为0.6mL/min。流动相：5％-95％(含0.1％甲酸的乙腈)在(含0.1％甲酸的水)中的比例)，采用电喷雾电离(ESI)，在210nm/254nm下，用UV检测。In each synthesis example, the measurement conditions of low-resolution mass spectrometry (MS) data are: Agilent 6120 quadrupole HPLC-M (column model: Zorbax SB-C18, 2.1×30mm, 3.5 microns, 6min, flow rate is 0.6mL/ min. Mobile phase: the ratio of 5%-95% (acetonitrile containing 0.1% formic acid) in (water containing 0.1% formic acid) using electrospray ionization (ESI), and UV detection at 210nm/254nm.
核磁共振氢谱：布鲁克(Bruker)400MHz核磁仪，室温条件下，以CD 2Cl 2为溶剂(以ppm为单位)，用TMS(0ppm)作为参照标准。当出现多重峰的时候，将使用下面的缩写：s(singlet，单峰)、d(doublet，双峰)、t(triplet，三重峰)、m(multiplet，多重峰)。 Proton nuclear magnetic resonance spectrum: Bruker 400MHz nuclear magnetic instrument, at room temperature, with CD 2 Cl 2 as the solvent (in ppm), and TMS (0 ppm) as the reference standard. When multiple peaks appear, the following abbreviations will be used: s (singlet, singlet), d (doublet, doublet), t (triplet, triplet), m (multiplet, multiplet).
目标化合物使用Agilent 1260pre-HPLC或Calesep pump 250pre-HPLC(柱子型号：NOVASEP50/80mm DAC)，在210nm/254nm用UV检测。The target compound uses Agilent 1260pre-HPLC or Calesep pump 250pre-HPLC (column model: NOVASEP50/80mm DAC), with UV detection at 210nm/254nm.
使用以下方法进行本申请的化合物的合成：The following methods were used to synthesize the compounds of this application:
Figure PCTCN2020122273-appb-000071
Figure PCTCN2020122273-appb-000071
将1-溴-2碘萘(40g；120.12mmol)、3-氯苯硼酸(20.7g；132.13mmol)、四(三苯基膦)钯(2.8g；2.4mmol)、碳酸钾(41.5g；300.3mmol)、四丁基溴化铵(7.7g；24.0mmol)加入烧瓶中，并加入甲苯(320mL)、乙醇(80mL)和水(80mL)的混合溶剂，氮气保护下，升温至80℃，保持温度搅拌8小时；冷却至室温，停止搅拌，反应液水洗后分离有机相，使用无水硫酸镁干燥，减压除去溶剂，得到粗品；使用正庚烷作为流动相对粗品进行硅胶柱色谱提纯，得到浅灰色固体产物中间体a-1(26.7g；收率70％)。Mix 1-bromo-2-iodonaphthalene (40g; 120.12mmol), 3-chlorophenylboronic acid (20.7g; 132.13mmol), tetrakis(triphenylphosphine) palladium (2.8g; 2.4mmol), potassium carbonate (41.5g; 300.3mmol), tetrabutylammonium bromide (7.7g; 24.0mmol) were added to the flask, and a mixed solvent of toluene (320mL), ethanol (80mL) and water (80mL) was added. Under nitrogen protection, the temperature was raised to 80°C, Keep the temperature and stir for 8 hours; cool to room temperature, stop stirring, separate the organic phase after washing the reaction solution with water, dry with anhydrous magnesium sulfate, remove the solvent under reduced pressure to obtain the crude product; use n-heptane as the mobile phase crude product for silica gel column chromatography purification, A light gray solid product intermediate a-1 (26.7 g; yield 70%) was obtained.
使用与合成中间体a-1类似的方法，使用表1中反应物A所示的化合物替代1-溴-2碘萘，反应物B所示的化合物替代3-氯苯硼酸，合成中间体b-1至中间体k-1：Using a method similar to the synthesis of intermediate a-1, using the compound shown in reactant A in Table 1 to replace 1-bromo-2-iodonaphthalene, and the compound shown in reactant B to replace 3-chlorophenylboronic acid to synthesize intermediate b -1 to intermediate k-1:
表1：中间体b-1至中间体k-1的合成Table 1: Synthesis of Intermediate b-1 to Intermediate K-1
Figure PCTCN2020122273-appb-000072
Figure PCTCN2020122273-appb-000072
Figure PCTCN2020122273-appb-000073
Figure PCTCN2020122273-appb-000073
将中间体a-1(26.7g，84.1mmol)和四氢呋喃(220mL)加入烧瓶中，氮气保护下，降温至-78℃，于搅拌条件下，滴加正丁基锂的四氢呋喃(2.5M)溶液(50mL，126.1mmol)，滴加完毕后保温搅拌1小时，保持-78℃滴加溶有金刚烷酮(10.1g，67.2mmol)的四氢呋喃(50mL)溶液，滴加完毕后保温1小时后升至室温，搅拌24小时，向反应液中加入盐酸(12M)(15mL，189.1mmol)的水(60mL)溶液，搅拌1小时，分液，有机相使用水洗至中性，加入无水硫酸镁干燥，减压除去溶剂得到粗品，使用乙酸乙酯/正庚烷体系对粗品进行硅胶柱色谱提纯，得到白色固体产物中间体a-2(16.3g，收率50％)。Add Intermediate a-1 (26.7g, 84.1mmol) and tetrahydrofuran (220mL) into the flask, under the protection of nitrogen, reduce the temperature to -78℃, under stirring conditions, add dropwise a solution of n-butyllithium in tetrahydrofuran (2.5M) (50mL, 126.1mmol), keep stirring for 1 hour after the addition is complete, add dropwise a tetrahydrofuran (50mL) solution with adamantanone (10.1g, 67.2mmol) dissolved in it at -78℃. After the addition is complete, keep it warm for 1 hour and then increase Bring to room temperature, stir for 24 hours, add hydrochloric acid (12M) (15mL, 189.1mmol) in water (60mL) to the reaction solution, stir for 1 hour, separate the layers, wash the organic phase with water to neutrality, add anhydrous magnesium sulfate to dry The solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using an ethyl acetate/n-heptane system to obtain a white solid product intermediate a-2 (16.3 g, yield 50%).
使用与合成中间体a-2类似的方法，使用表2中所示的反应物C替代中间体a-1，合成中间体b-2至中间体k-2：Using a method similar to the synthesis of intermediate a-2, using reactant C shown in Table 2 instead of intermediate a-1, intermediate b-2 to intermediate k-2 were synthesized:
表2：中间体b-2至中间体k-2的合成Table 2: Synthesis of Intermediate b-2 to Intermediate K-2
Figure PCTCN2020122273-appb-000074
Figure PCTCN2020122273-appb-000074
Figure PCTCN2020122273-appb-000075
Figure PCTCN2020122273-appb-000075
Figure PCTCN2020122273-appb-000076
Figure PCTCN2020122273-appb-000076
将中间体a-2(16.3g，41.9mmol)和冰醋酸(165mL)加入烧瓶中，氮气保护常温搅拌条件下缓慢滴加浓硫酸(98％)(0.8mL，8.4mmol)的醋酸(20mL)溶液，滴加完毕后升至80℃，搅拌2小时；降至室温，过滤析出的固体，使用水和乙醇淋洗滤饼，烘干得到粗品；使用二氯甲烷/正庚烷体系对粗品进行硅胶柱色谱提纯，得到白色固体中间体a-3(10.9g，收率70％)。Add Intermediate a-2 (16.3g, 41.9mmol) and glacial acetic acid (165mL) into the flask, slowly add concentrated sulfuric acid (98%) (0.8mL, 8.4mmol) and acetic acid (20mL) under nitrogen protection at room temperature and stirring. After the addition of the solution, increase to 80°C and stir for 2 hours; reduce to room temperature, filter the precipitated solid, rinse the filter cake with water and ethanol, and dry to obtain the crude product; use the dichloromethane/n-heptane system to perform the crude product Purification by silica gel column chromatography gave a white solid intermediate a-3 (10.9 g, yield 70%).
以下表3中反应物D替代中间体a-2，使用上述类似的方法合成中间体b-3至k-3：The reactant D in the following Table 3 replaces the intermediate a-2, and the intermediates b-3 to k-3 are synthesized using the above-mentioned similar method:
表3：中间体b-3至中间体k-3的合成Table 3: Synthesis of Intermediate b-3 to Intermediate K-3
Figure PCTCN2020122273-appb-000077
Figure PCTCN2020122273-appb-000077
Figure PCTCN2020122273-appb-000078
Figure PCTCN2020122273-appb-000078
Figure PCTCN2020122273-appb-000079
Figure PCTCN2020122273-appb-000079
将中间体a-3(10.9g，29.4mmol)，联硼酸频哪醇酯(9.0g，35.3mmol)、三(二亚苄基丙酮)二钯(0.27g，0.29mmol)、2-二环己基磷-2',4',6'-三异丙基联苯(0.27g，0.58mmol)、醋酸钾(8.65g，88.1mmol)和1,4-二氧六环(80mL)加入烧瓶中，氮气保护条件下于100℃回流搅拌16小时；降至室温，向反应液中加入二氯甲烷和水，分液，有机相使用水洗后用无水硫酸镁干燥，减压条件下除去溶剂得到粗品；粗品使用二氯甲烷/正庚烷体系进行硅胶柱色谱提纯，得到白色固体中间体a-4(7.5g，收率55％)。Intermediate a-3 (10.9g, 29.4mmol), pinacol diborate (9.0g, 35.3mmol), tris(dibenzylideneacetone) dipalladium (0.27g, 0.29mmol), 2-bicyclo Hexylphosphorus-2',4',6'-triisopropylbiphenyl (0.27g, 0.58mmol), potassium acetate (8.65g, 88.1mmol) and 1,4-dioxane (80mL) were added to the flask , Under nitrogen protection, reflux and stir at 100°C for 16 hours; reduce to room temperature, add dichloromethane and water to the reaction solution, separate the liquids, wash the organic phase with water and then dry with anhydrous magnesium sulfate, and remove the solvent under reduced pressure. Crude product: The crude product was purified by silica gel column chromatography using a dichloromethane/n-heptane system to obtain a white solid intermediate a-4 (7.5 g, yield 55%).
以下表4中反应物E替代中间体a-3，使用上述类似的方法合成中间体b-4至i-4：The reactant E in the following Table 4 replaces the intermediate a-3, and the intermediates b-4 to i-4 are synthesized using the above-mentioned similar method:
表4：中间体b-4至中间体i-4的合成Table 4: Synthesis of Intermediate b-4 to Intermediate i-4
Figure PCTCN2020122273-appb-000080
Figure PCTCN2020122273-appb-000080
Figure PCTCN2020122273-appb-000081
Figure PCTCN2020122273-appb-000081
Figure PCTCN2020122273-appb-000082
Figure PCTCN2020122273-appb-000082
将中间体k-3(7g,20.8mmol)、N-溴代丁二酰亚胺(7.4g,41.6mmol)加入烧瓶中，并加入DMF(N,N-二甲基甲酰胺)(70mL)作溶剂，氮气保护下，升温至80℃，保持温度搅拌16小时；冷却至室温，停止搅拌，反应液水洗后分离有机相，使用无水硫酸镁干燥，减压除去溶剂，得到粗品；使用二氯甲烷/正庚烷混合溶剂作为流动相对粗品进行硅胶柱色谱提纯，得到白色固体产物中间体k-4(6.47g,收率75％)。Intermediate k-3 (7g, 20.8mmol), N-bromosuccinimide (7.4g, 41.6mmol) were added to the flask, and DMF (N,N-dimethylformamide) (70mL) was added As a solvent, under the protection of nitrogen, the temperature is increased to 80°C, and the temperature is kept stirring for 16 hours; cooled to room temperature, the stirring is stopped, the reaction solution is washed with water, and the organic phase is separated, dried with anhydrous magnesium sulfate, and the solvent is removed under reduced pressure to obtain the crude product; The methyl chloride/n-heptane mixed solvent was used as the mobile phase and the crude product was purified by silica gel column chromatography to obtain a white solid product intermediate k-4 (6.47 g, yield 75%).
以下表5中反应物F替代中间体k-3，使用上述类似的方法合成中间体j-4：The reactant F in the following Table 5 replaces intermediate k-3, and the intermediate j-4 is synthesized using the above-mentioned similar method:
表5：中间体j-4的合成Table 5: Synthesis of intermediate j-4
Figure PCTCN2020122273-appb-000083
Figure PCTCN2020122273-appb-000083
Figure PCTCN2020122273-appb-000084
Figure PCTCN2020122273-appb-000084
将中间体k-4(6.4g，15.4mmol)，联硼酸频哪醇酯(4.3g，16.9mmol)、[1,1'-双(二苯基膦基)二茂铁]二氯化钯(0.23g，0.31mmol)、醋酸钾(3.02g，30.8mmol)和1,4-二氧六环(65mL)加入烧瓶中，氮气保护条件下于100℃回流搅拌6小时；降至室温，向反应液中加入二氯甲烷和水，分液，有机相使用水洗后用无水硫酸镁干燥，减压条件下除去溶剂得到粗品；粗品使用二氯甲烷/正庚烷体系进行硅胶柱色谱提纯，得到白色固体中间体k-5(4.8g，收率68％)。Intermediate k-4 (6.4g, 15.4mmol), pinacol diborate (4.3g, 16.9mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.23g, 0.31mmol), potassium acetate (3.02g, 30.8mmol) and 1,4-dioxane (65mL) were added to the flask, and refluxed and stirred at 100°C for 6 hours under nitrogen protection; cooled to room temperature, Dichloromethane and water were added to the reaction solution for liquid separation. The organic phase was washed with water and dried with anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain a crude product; the crude product was purified by silica gel column chromatography using a dichloromethane/n-heptane system. A white solid intermediate k-5 (4.8 g, yield 68%) was obtained.
以下表6中反应物F替代中间体k-3，使用上述类似的方法合成中间体j-5：The reactant F in the following Table 6 replaces intermediate k-3, and the intermediate j-5 is synthesized using the above-mentioned similar method:
表6：中间体j-5的合成Table 6: Synthesis of intermediate j-5
Figure PCTCN2020122273-appb-000085
Figure PCTCN2020122273-appb-000085
Figure PCTCN2020122273-appb-000086
Figure PCTCN2020122273-appb-000086
将中间体a-4(7.5g；16.2mmol)、3-溴咔唑(4.2g；17.0mmol)，四(三苯基膦)钯(0.4g；0.3mmol)，碳酸钾(5.6g；40.5mmol)，四丁基溴化铵(1.0g；3.2mmol)加入烧瓶中，并加入甲苯(80mL)、乙醇(20mL)和水(20mL)的混合溶剂，氮气保护下，升温至80℃，保持温度搅拌12小时；冷却至室温，停止搅拌，反应液水洗后分离有机相，使用无水硫酸镁干燥，减压除去溶剂，得到粗品；使用二氯甲烷/正庚烷混合溶剂作为流动相对粗品进行硅胶柱色谱提纯，得到白色固体产物中间体M-1(6.09g；收率75％)Intermediate a-4 (7.5g; 16.2mmol), 3-bromocarbazole (4.2g; 17.0mmol), tetrakis(triphenylphosphine) palladium (0.4g; 0.3mmol), potassium carbonate (5.6g; 40.5 mmol), tetrabutylammonium bromide (1.0g; 3.2mmol) was added to the flask, and a mixed solvent of toluene (80mL), ethanol (20mL) and water (20mL) was added. Stir at temperature for 12 hours; cool to room temperature, stop stirring, wash the reaction solution with water, separate the organic phase, dry with anhydrous magnesium sulfate, remove the solvent under reduced pressure to obtain a crude product; use a dichloromethane/n-heptane mixed solvent as the mobile relative crude product Purified by silica gel column chromatography to obtain a white solid product intermediate M-1 (6.09g; yield 75%)
使用与合成中间体A类似的方法，使用表7中所示的反应物H替代中间体a-4，用表7中所示的反应物I替代3-溴咔唑，合成中间体2～29：Using a method similar to the synthesis of intermediate A, using reactant H shown in Table 7 instead of intermediate a-4, and using reactant I shown in Table 7 instead of 3-bromocarbazole to synthesize intermediates 2-29 :
表7：中间体2至29的合成Table 7: Synthesis of Intermediates 2 to 29
Figure PCTCN2020122273-appb-000087
Figure PCTCN2020122273-appb-000087
Figure PCTCN2020122273-appb-000088
Figure PCTCN2020122273-appb-000088
Figure PCTCN2020122273-appb-000089
Figure PCTCN2020122273-appb-000089
Figure PCTCN2020122273-appb-000090
Figure PCTCN2020122273-appb-000090
Figure PCTCN2020122273-appb-000091
Figure PCTCN2020122273-appb-000091
Figure PCTCN2020122273-appb-000092
Figure PCTCN2020122273-appb-000092
将中间体M-1(6.09g；mmol)，2-(3-溴苯基)二苯并呋喃(4.7g；14.6mmol)，碘化亚铜(0.3g；2.4mmol)，碳酸钾(3.7g；26.7mmol)，1,10-菲啰啉(0.9g；4.8mmol)，18-冠-6-醚(0.3g；1.2mmol)和二甲基甲酰胺(40mL)加入烧瓶中，氮气保护下升温至145℃，搅拌8小时；降至室温，向反应液 中加入二氯甲烷(80mL)和水(100mL)，分液，有机相水洗后加入无水硫酸镁干燥，减压除去溶剂得到粗品；粗品使用二氯甲烷/正庚烷体系进行硅胶柱色谱提纯后，使用二氯甲烷/乙酸乙酯体系进行重结晶提纯，得到白色固体产物化合物20(4.5g；收率50％)。Intermediate M-1 (6.09g; mmol), 2-(3-bromophenyl) dibenzofuran (4.7g; 14.6mmol), cuprous iodide (0.3g; 2.4mmol), potassium carbonate (3.7 g; 26.7mmol), 1,10-phenanthroline (0.9g; 4.8mmol), 18-crown-6-ether (0.3g; 1.2mmol) and dimethylformamide (40mL) were added to the flask under nitrogen protection The temperature was raised to 145°C and stirred for 8 hours; the temperature was lowered to room temperature, dichloromethane (80mL) and water (100mL) were added to the reaction solution, the liquids were separated, the organic phase was washed with water and dried by adding anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Crude product: After the crude product was purified by silica gel column chromatography using a dichloromethane/n-heptane system, it was purified by recrystallization using a dichloromethane/ethyl acetate system to obtain a white solid product compound 20 (4.5 g; yield 50%).
使用与合成化合物20类似的方法，使用表8中反应物J替代中间体M-1，使用表8中反应物K替代2-(3-溴苯基)二苯并呋喃，合成下表8中所示化合物：Using a method similar to the synthesis of compound 20, using reactant J in Table 8 instead of intermediate M-1, and using reactant K in Table 8 instead of 2-(3-bromophenyl)dibenzofuran, the synthesis in Table 8 below Shown compound:
表8：部分化合物的结构和原料Table 8: Structures and raw materials of some compounds
Figure PCTCN2020122273-appb-000093
Figure PCTCN2020122273-appb-000093
Figure PCTCN2020122273-appb-000094
Figure PCTCN2020122273-appb-000094
Figure PCTCN2020122273-appb-000095
Figure PCTCN2020122273-appb-000095
Figure PCTCN2020122273-appb-000096
Figure PCTCN2020122273-appb-000096
将中间体6(6g；12.0mmol)、2-氯-4,6-二苯基-1,3,5-三嗪(3.5g；13.1mmol)、4-二甲氨基吡啶(0.7g；6.0mmol)、碳酸铯(3.9g；12.0mmol)和二甲基亚砜(80mL)加入圆底烧瓶中，氮气保护条件下，搅拌升温至100℃，反应12小时；反应结束后降至室温，过滤，滤饼使用水和乙醇淋洗，烘干得到粗品；对粗品使用甲苯/正庚烷体系进行重结晶提纯，得到浅黄色固体化合物26(5.2g；收率60％)。Intermediate 6 (6g; 12.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.5g; 13.1mmol), 4-dimethylaminopyridine (0.7g; 6.0 mmol), cesium carbonate (3.9g; 12.0mmol) and dimethyl sulfoxide (80mL) were added to a round-bottomed flask. Under nitrogen protection, the mixture was stirred and heated to 100°C and reacted for 12 hours; after the reaction, it was cooled to room temperature and filtered The filter cake was rinsed with water and ethanol, and dried to obtain a crude product; the crude product was purified by recrystallization using a toluene/n-heptane system to obtain a pale yellow solid compound 26 (5.2 g; yield 60%).
使用与合成化合物26类似的方法，使用表9中反应物L替代中间体M-6，反应物M替代2-氯-4,6-二苯基-1,3,5-三嗪，合成下表9中所示化合物：Using a method similar to the synthesis of compound 26, using reactant L in Table 9 instead of intermediate M-6, and reactant M instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, the synthesis is as follows Compounds shown in Table 9:
表9：部分化合物的原料和结构Table 9: Raw materials and structures of some compounds
Figure PCTCN2020122273-appb-000097
Figure PCTCN2020122273-appb-000097
Figure PCTCN2020122273-appb-000098
Figure PCTCN2020122273-appb-000098
对以上化合物进行质谱分析，得到数据如下表10所示：The above compounds were analyzed by mass spectrometry, and the data obtained are shown in Table 10 below:
表10：部分化合物的质谱数据Table 10: Mass spectrum data of some compounds
化合物2Compound 2 m/z＝654.3[M+H] + m/z=654.3[M+H] + 化合物89Compound 89 m/z＝733.3[M+H] + m/z=733.3[M+H] +
化合物6Compound 6 m/z＝607.3[M+H] + m/z=607.3[M+H] + 化合物99Compound 99 m/z＝634.3[M+H] + m/z=634.3[M+H] +
化合物12Compound 12 m/z＝730.3[M+H] + m/z=730.3[M+H] + 化合物103Compound 103 m/z＝694.3[M+H] + m/z=694.3[M+H] +
化合物14Compound 14 m/z＝725.3[M+H] + m/z=725.3[M+H] + 化合物107Compound 107 m/z＝885.4[M+H] + m/z=885.4[M+H] +
化合物20Compound 20 m/z＝744.3[M+H] + m/z=744.3[M+H] + 化合物110Compound 110 m/z＝839.3[M+H] + m/z=839.3[M+H] +
化合物21Compound 21 m/z＝760.3[M+H] + m/z=760.3[M+H] + 化合物113Compound 113 m/z＝809.4[M+H] + m/z=809.4[M+H] +
化合物26Compound 26 m/z＝733.3[M+H] + m/z=733.3[M+H] + 化合物125Compound 125 m/z＝746.3[M+H] + m/z=746.3[M+H] +
化合物31Compound 31 m/z＝704.3[M+H] + m/z=704.3[M+H] + 化合物131Compound 131 m/z＝758.3[M+H] + m/z=758.3[M+H] +
化合物33Compound 33 m/z＝743.3[M+H] + m/z=743.3[M+H] + 化合物136Compound 136 m/z＝809.4[M+H] + m/z=809.4[M+H] +
化合物38Compound 38 m/z＝668.3[M+H] + m/z=668.3[M+H] + 化合物142Compound 142 m/z＝668.3[M+H] + m/z=668.3[M+H] +
化合物57Compound 57 m/z＝678.3[M+H] + m/z=678.3[M+H] + 化合物147Compound 147 m/z＝706.3[M+H] + m/z=706.3[M+H] +
化合物78Compound 78 m/z＝770.4[M+H] + m/z=770.4[M+H] + 化合物153Compound 153 m/z＝823.3[M+H] + m/z=823.3[M+H] +
化合物83Compound 83 m/z＝678.3[M+H] + m/z=678.3[M+H] + 化合物157Compound 157 m/z＝732.3[M+H] + m/z=732.3[M+H] +
化合物88Compound 88 m/z＝822.4[M+H] + m/z=822.4[M+H] + 化合物222Compound 222 m/z＝756.3[M+H] + m/z=756.3[M+H] +
化合物95Compound 95 m/z＝672.3[M+H] + m/z=672.3[M+H] +  To  To
部分上述实施例化合物的核磁数据：NMR data of some of the compounds in the above examples:
化合物2： 1HNMR(CD 2Cl 2,400MHz)δ(ppm):8.26(d,1H),7.91-7.84(m,3H),7.79-7.49(m,4H),7.61-7.52(m,9H),7.42-7.38(m,3H),7.33-7.24(m,5H),2.80(d,2H),2.71(d,2H),2.15(s,1H),2.14(s,1H),1.93(s,2H),1.72(t,4H),1.42(s,2H). Compound 2: 1 HNMR (CD 2 Cl 2 , 400MHz) δ (ppm): 8.26 (d, 1H), 7.91-7.84 (m, 3H), 7.79-7.49 (m, 4H), 7.61-7.52 (m, 9H) ), 7.42-7.38(m, 3H), 7.33-7.24(m, 5H), 2.80(d, 2H), 2.71(d, 2H), 2.15(s, 1H), 2.14(s, 1H), 1.93( s, 2H), 1.72 (t, 4H), 1.42 (s, 2H).
化合物20： 1HNMR(CD 2Cl 2,400MHz)δ(ppm):8.29(d,1H),8.12(s,1H),8.06(s,1H),8.01(d,1H),7.96-7.94(m,2H),7.88-7.83(m,2H),7.78(d,1H),7.71(d,1H),7.61-7.54(m,5H),7.52-7.45(m,3H),7.42-7.36(m,2H),7.34-7.20(m,5H),7.12(d,1H),7.08(d,1H),2.83(d,2H),2.74(d,2H),2.16(s,1H),2.10(s,1H),1.95(s,2H),1.75(t,4H),1.40(s,2H). Compound 20: 1 HNMR (CD 2 Cl 2 , 400MHz) δ (ppm): 8.29 (d, 1H), 8.12 (s, 1H), 8.06 (s, 1H), 8.01 (d, 1H), 7.96-7.94 ( m,2H),7.88-7.83(m,2H),7.78(d,1H),7.71(d,1H),7.61-7.54(m,5H),7.52-7.45(m,3H),7.42-7.36( m, 2H), 7.34-7.20 (m, 5H), 7.12 (d, 1H), 7.08 (d, 1H), 2.83 (d, 2H), 2.74 (d, 2H), 2.16 (s, 1H), 2.10 (s, 1H), 1.95 (s, 2H), 1.75 (t, 4H), 1.40 (s, 2H).
化合物26： 1HNMR(CD 2Cl 2,400MHz)δ(ppm):8.53-8.51(m,4H),8.36(s,1H),8.26(d,2H),8.05(d,1H),7.95(m,1H),7.88-7.84(m,2H),7.79(d,1H),7.71(d,1H),7.58-7.54(m,7H),7.43(d,1H),7.42-7.38(m,2H),7.27(t,1H),7.00(d,1H),6.90(d,1H),2.86(d,2H),2.74(d,2H),2.15(s,1H),2.09(s,1H),1.95(s,2H),1.72(t,4H),1.43(s,2H). Compound 26: 1 HNMR (CD 2 Cl 2 , 400MHz) δ (ppm): 8.53-8.51 (m, 4H), 8.36 (s, 1H), 8.26 (d, 2H), 8.05 (d, 1H), 7.95 ( m, 1H), 7.88-7.84 (m, 2H), 7.79 (d, 1H), 7.71 (d, 1H), 7.58-7.54 (m, 7H), 7.43 (d, 1H), 7.42-7.38 (m, 2H), 7.27(t, 1H), 7.00(d, 1H), 6.90(d, 1H), 2.86(d, 2H), 2.74(d, 2H), 2.15(s, 1H), 2.09(s, 1H) ), 1.95(s, 2H), 1.72(t, 4H), 1.43(s, 2H).
化合物99： 1HNMR(CD 2Cl 2,400MHz)δ(ppm):8.36(s,1H),8.17(s,1H),8.07(m,1H),7.90(t,2H),7.79(d,1H),7.62(s,1H),7.52(t,1H),7.47-7.40(m,4H),7.30-7.24(m,6H),7.02-6.94(m,2H),2.84(d,2H),2.71(d,2H),2.13(s,1H),2.11(s,1H),1.90(s,2H),1.74(t,4H),1.38(s,2H),1.33(s,9H). Compound 99: 1 HNMR (CD 2 Cl 2 , 400MHz) δ (ppm): 8.36 (s, 1H), 8.17 (s, 1H), 8.07 (m, 1H), 7.90 (t, 2H), 7.79 (d, 1H), 7.62 (s, 1H), 7.52 (t, 1H), 7.47-7.40 (m, 4H), 7.30-7.24 (m, 6H), 7.02-6.94 (m, 2H), 2.84 (d, 2H) , 2.71 (d, 2H), 2.13 (s, 1H), 2.11 (s, 1H), 1.90 (s, 2H), 1.74 (t, 4H), 1.38 (s, 2H), 1.33 (s, 9H).
有机电致发光器件的制备和性能评估Preparation and performance evaluation of organic electroluminescent devices
实施例1：绿色有机电致发光器件Example 1: Green organic electroluminescent device
使用以下方法进行绿色有机电致发光器件的制作：Use the following methods to make green organic electroluminescent devices:
通过以下过程制备阳极：将ITO厚度为
Figure PCTCN2020122273-appb-000099
的ITO基板切割成40mm(长)×40mm(宽)×0.7mm(厚)的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，并可利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极的功函数，并可采用有机溶剂清洗ITO基板表面，以清除ITO基板表面的杂质及油污。需要说明的是，ITO基板还可以根据实际需要切割成其他尺寸，在此不对本申请中ITO基板的尺寸做特殊限定。 The anode is prepared by the following process: the thickness of ITO is
Figure PCTCN2020122273-appb-000099
The ITO substrate is cut into a size of 40mm (length) × 40mm (width) × 0.7mm (thickness), and the photolithography process is used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns, and can use ultraviolet ozone and O 2 :N 2 plasma is used for surface treatment to increase the work function of the anode, and organic solvents can be used to clean the surface of the ITO substrate to remove impurities and grease on the surface of the ITO substrate. It should be noted that the ITO substrate can also be cut into other sizes according to actual needs, and the size of the ITO substrate in this application is not specifically limited here.
在实验基板(阳极)上真空蒸镀F4-TCNQ以形成厚度为
Figure PCTCN2020122273-appb-000100
的空穴注入层(HIL)，并且在空穴注入层蒸镀HT-01，形成厚度为
Figure PCTCN2020122273-appb-000101
的第一空穴传输层。 F4-TCNQ was vacuum evaporated on the experimental substrate (anode) to form a thickness of
Figure PCTCN2020122273-appb-000100
The hole injection layer (HIL), and HT-01 is vapor-deposited on the hole injection layer to form a thickness of
Figure PCTCN2020122273-appb-000101
The first hole transport layer.
在第一空穴传输层上真空蒸镀HT-02，形成厚度为
Figure PCTCN2020122273-appb-000102
的第二空穴传输层。 Vacuum evaporate HT-02 on the first hole transport layer to form a thickness of
Figure PCTCN2020122273-appb-000102
The second hole transport layer.
在第二空穴传输层上，将化合物2：GH-n1：Ir(ppy) 3以50％：45％：5％(蒸镀速率)的比例进行共同蒸镀，形成厚度为
Figure PCTCN2020122273-appb-000103
的绿色发光层(EML)。 On the second hole transport layer, the compound 2: GH-n1: Ir(ppy) 3 was co-evaporated at a ratio of 50%: 45%: 5% (evaporation rate) to form a thickness of
Figure PCTCN2020122273-appb-000103
The green light-emitting layer (EML).
将ET-01和LiQ以1:1的重量比进行混合并蒸镀形成了
Figure PCTCN2020122273-appb-000104
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020122273-appb-000105
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1：9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020122273-appb-000106
的阴极。 ET-01 and LiQ were mixed at a weight ratio of 1:1 and evaporated to form
Figure PCTCN2020122273-appb-000104
Thick electron transport layer (ETL), LiQ is vapor-deposited on the electron transport layer to form a thickness of
Figure PCTCN2020122273-appb-000105
The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at an evaporation rate of 1:9, and then vacuum-evaporated on the electron injection layer to form a thickness of
Figure PCTCN2020122273-appb-000106
The cathode.
此外，在上述阴极上蒸镀厚度为
Figure PCTCN2020122273-appb-000107
的CP-01，形成有机覆盖层(CPL)，从而完成有机发光器件的制造。 In addition, the vapor deposition thickness on the above cathode is
Figure PCTCN2020122273-appb-000107
CP-01 to form an organic cover layer (CPL), thereby completing the manufacture of organic light-emitting devices.
实施例2-实施16Example 2-Implementation 16
除了利用表10中化合物N列所示的化合物，替换实施例1中的化合物2外，采用与实施例1相同的方法制备有机电致发光器件。其中，在所制备的有机电致发光器件的有机发光层中，化合物N：GH-n1:Ir(ppy) 3＝50％:45％:5％。例如，在实施例2中，化合物N为化合物6，利用化合物6替代实施例1中的化合物2以制备有机电致发光器件。 Except that the compound shown in the column of compound N in Table 10 was used instead of compound 2 in Example 1, the same method as in Example 1 was used to prepare an organic electroluminescent device. Wherein, in the organic light-emitting layer of the prepared organic electroluminescence device, compound N: GH-n1: Ir(ppy) 3 = 50%: 45%: 5%. For example, in Example 2, compound N is compound 6, and compound 6 is used instead of compound 2 in Example 1 to prepare an organic electroluminescence device.
比较例1-比较例4Comparative Example 1-Comparative Example 4
除了在形成发光层时，以下表中所示的化合物A-D替代实施例1中化合物2以外，采用与实施例1相同的方法制备有机电致发光器件。例如，在比较例1中，在所制备的有机电致发光器件的有机发光层中，化合物A：GH-n1:Ir(ppy) 3＝50％:45％:5％。 Except that when forming the light-emitting layer, the compound AD shown in the following table replaces the compound 2 in Example 1, and the organic electroluminescent device is prepared by the same method as in Example 1. For example, in Comparative Example 1, in the organic light-emitting layer of the prepared organic electroluminescence device, compound A: GH-n1: Ir(ppy) 3 = 50%: 45%: 5%.
其中，在实施例1-16及比较例1-4中使用的材料结构如下所示：Among them, the material structures used in Examples 1-16 and Comparative Examples 1-4 are as follows:
Figure PCTCN2020122273-appb-000108
Figure PCTCN2020122273-appb-000108
Figure PCTCN2020122273-appb-000109
Figure PCTCN2020122273-appb-000109
对实施例1～16和比较例1～4所制备的有机电致发光器件，在20mA/cm 2的条件下进行性能测试，测试结果如下表11中。 The organic electroluminescent devices prepared in Examples 1 to 16 and Comparative Examples 1 to 4 were tested for performance under the condition of 20 mA/cm 2. The test results are shown in Table 11 below.
表11：有机电致发光器件的性能测试结果Table 11: Performance test results of organic electroluminescent devices
Figure PCTCN2020122273-appb-000110
Figure PCTCN2020122273-appb-000110
Figure PCTCN2020122273-appb-000111
Figure PCTCN2020122273-appb-000111
根据表11所示的数据可知，相较于比较例1～4所制备的有机电致发光器件，实施例1～16所制备的有机电致发光器件在驱动电压相近的前提下，其发光效率有了一定改善，器件寿命至少提高了50％。因此，本申请的含氮化合物用作有机电致发光器件的有机发光层材料时，尤其是用作有机电致发光器件的有机发光层的主体材料时，可以改善有机电致发光器件的效率性能和寿命。According to the data shown in Table 11, compared with the organic electroluminescent devices prepared in Comparative Examples 1 to 4, the organic electroluminescent devices prepared in Examples 1 to 16 have similar luminous efficiency under the premise of similar driving voltages. With a certain improvement, the life of the device has been increased by at least 50%. Therefore, when the nitrogen-containing compound of the present application is used as an organic light-emitting layer material of an organic electroluminescence device, especially when used as a host material of an organic light-emitting layer of an organic electroluminescence device, the efficiency performance of the organic electroluminescence device can be improved And longevity.
实施例17：红色有机电致发光器件Example 17: Red organic electroluminescent device
通过以下过程制备阳极：将ITO厚度为
Figure PCTCN2020122273-appb-000112
的ITO基板切割成40mm(长)×40mm(宽)×0.7mm(厚)的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，并可利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极的功函数，并可采用有机溶剂清洗ITO基板表面，以清除ITO基板表面的杂质及油污。需要说明的是，ITO基板还可以根据实际需要切割成其他尺寸，在此不对本申请中ITO基板的尺寸做特殊限定。 The anode is prepared by the following process: the thickness of ITO is
Figure PCTCN2020122273-appb-000112
The ITO substrate is cut into a size of 40mm (length) × 40mm (width) × 0.7mm (thickness), and the photolithography process is used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns, and can use ultraviolet ozone and O 2 :N 2 plasma is used for surface treatment to increase the work function of the anode, and organic solvents can be used to clean the surface of the ITO substrate to remove impurities and grease on the surface of the ITO substrate. It should be noted that the ITO substrate can also be cut into other sizes according to actual needs, and the size of the ITO substrate in this application is not specifically limited here.
在实验基板(阳极)上真空蒸镀F4-TCNQ以形成厚度为的厚度为
Figure PCTCN2020122273-appb-000113
的空穴注入层(HIL)，并且在空穴注入层蒸镀HT-01，形成厚度为
Figure PCTCN2020122273-appb-000114
的第一空穴传输层。 F4-TCNQ was vacuum-evaporated on the experimental substrate (anode) to form a thickness of
Figure PCTCN2020122273-appb-000113
The hole injection layer (HIL), and HT-01 is vapor-deposited on the hole injection layer to form a thickness of
Figure PCTCN2020122273-appb-000114
The first hole transport layer.
在第一空穴传输层上真空蒸镀HT-03，形成厚度为
Figure PCTCN2020122273-appb-000115
的第二空穴传输层。 Vacuum evaporate HT-03 on the first hole transport layer to form a thickness of
Figure PCTCN2020122273-appb-000115
The second hole transport layer.
在第二空穴传输层上，将化合物26：Ir(piq) 2(acac)以95％：5％(蒸镀速率)的比例进行共同蒸镀，形成厚度为
Figure PCTCN2020122273-appb-000116
的红色发光层(EML)。 On the second hole transport layer, compound 26: Ir(piq) 2 (acac) was co-evaporated at a ratio of 95%: 5% (evaporation rate) to form a thickness of
Figure PCTCN2020122273-appb-000116
The red light-emitting layer (EML).
将ET-01和LiQ以1:1的重量比进行混合并蒸镀形成了
Figure PCTCN2020122273-appb-000117
厚的电子传输层(ETL)，将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020122273-appb-000118
的电子注入层(EIL)，然后将镁(Mg)和银(Ag)以1：9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020122273-appb-000119
的阴极。 ET-01 and LiQ were mixed at a weight ratio of 1:1 and evaporated to form
Figure PCTCN2020122273-appb-000117
Thick electron transport layer (ETL), LiQ is vapor-deposited on the electron transport layer to form a thickness of
Figure PCTCN2020122273-appb-000118
The electron injection layer (EIL) is then mixed with magnesium (Mg) and silver (Ag) at an evaporation rate of 1:9, and then vacuum-evaporated on the electron injection layer to form a thickness of
Figure PCTCN2020122273-appb-000119
The cathode.
此外，在上述阴极上蒸镀厚度为
Figure PCTCN2020122273-appb-000120
的CP-01，形成有机覆盖层(CPL)，从而完成有机发光器件的制造。 In addition, the vapor deposition thickness on the above cathode is
Figure PCTCN2020122273-appb-000120
CP-01 to form an organic cover layer (CPL), thereby completing the manufacture of organic light-emitting devices.
实施例18-实施例29Example 18-Example 29
除了利用表11中化合物M列所示的化合物，替换实施例17中的化合物26外，采用与实施例17相同的方法制备有机电致发光器件。其中，在所制备的有机电致发光器件的有机发光层中，化合物M：Ir(piq) 2(acac)＝95％:5％。例如，在实施例18中，化合物M为化合物88，利用化合物88替代实施例17中的化合物26以制备有机电致发光器件。 Except that the compound shown in the column of compound M in Table 11 was used instead of compound 26 in Example 17, the same method as in Example 17 was used to prepare an organic electroluminescent device. Wherein, in the organic light-emitting layer of the prepared organic electroluminescent device, compound M: Ir(piq) 2 (acac) = 95%: 5%. For example, in Example 18, compound M is compound 88, and compound 88 is used instead of compound 26 in Example 17 to prepare an organic electroluminescence device.
比较例5-比较例9Comparative Example 5-Comparative Example 9
除了在形成发光层时，以下表中所示的化合物E-H替代实施例17中化合物26以外，采用与实施例17相同的方法制备有机电致发光器件。例如，在比较例5中，在所制备的有机电致发光器件的有机发光层中，化合物E：Ir(piq) 2(acac)＝95％:5％。 Except that the compound EH shown in the following table replaced compound 26 in Example 17 when forming the light-emitting layer, the same method as in Example 17 was used to prepare an organic electroluminescent device. For example, in Comparative Example 5, in the organic light-emitting layer of the prepared organic electroluminescent device, compound E: Ir(piq) 2 (acac) = 95%: 5%.
以上实施例和对比例使用的部分材料结构如下所示：Some material structures used in the above embodiments and comparative examples are as follows:
Figure PCTCN2020122273-appb-000121
Figure PCTCN2020122273-appb-000121
对实施例17～29和比较例5～8所制备的有机电致发光器件，在20mA/cm 2的条件下进行性能测试，测试结果如下表12中。 The organic electroluminescent devices prepared in Examples 17-29 and Comparative Examples 5-8 were tested for performance under the condition of 20 mA/cm 2. The test results are shown in Table 12 below.
表12：有机电致发光器件的性能测试结果Table 12: Performance test results of organic electroluminescent devices
Figure PCTCN2020122273-appb-000122
Figure PCTCN2020122273-appb-000122
Figure PCTCN2020122273-appb-000123
Figure PCTCN2020122273-appb-000123
根据表12所示的数据可知，相较于比较例5～8所制备的有机电致发光器件，实施例17～29所制备的有机电致发光器件的驱动电压和发光效率有了一定改善，其器件发光效率至少提升10％，寿命至少提高了27％。因此，本申请的含氮化合物用作为有机电致发光器件的有机发光层材料时，尤其是用作有机电致发光器件的有机发光层的主体材料时，可以改善有机电致发光器件的效率性能和寿命性能。According to the data shown in Table 12, compared with the organic electroluminescent devices prepared in Comparative Examples 5-8, the driving voltage and luminous efficiency of the organic electroluminescent devices prepared in Examples 17-29 have been improved to a certain extent. The luminous efficiency of the device is increased by at least 10%, and the life span is increased by at least 27%. Therefore, when the nitrogen-containing compound of the present application is used as an organic light-emitting layer material of an organic electroluminescence device, especially when used as a host material of an organic light-emitting layer of an organic electroluminescence device, the efficiency performance of the organic electroluminescence device can be improved And life performance.
本申请化合物中，作为含氮化合物核心中一部分的金刚烷螺合稠合芴基，与咔唑基连接，使化合物整体具有较强的刚性并使得本申请的含氮化合物具有高的第一三重态能级，化合物中与稠合芴基共轭连接的咔唑环具有较好的空穴传输能力，因此本申请的含氮化合物适合作为有机电致发光器件中的发光层主体材料。含氮化合物具有高的空穴迁移率，有助于促进发光层中空穴和电子的传输平衡，改善有机电致发光器件的效率性能。电子和空穴在有机发光层中的复合率提升，减少或者避免电子穿过有机发光层而向空穴传输层传输，进而可以有效地保护空穴传输层材料免受电子的冲击，提高有机电致发光器件的寿命。In the compound of the present application, the adamantane spiro-fused fluorenyl group, which is part of the core of the nitrogen-containing compound, is connected to the carbazolyl group, so that the compound as a whole has strong rigidity and the nitrogen-containing compound of the present application has a high first three In the heavy state energy level, the carbazole ring conjugated to the fused fluorenyl group in the compound has a good hole transport ability, so the nitrogen-containing compound of the present application is suitable as the host material of the light-emitting layer in the organic electroluminescence device. Nitrogen-containing compounds have high hole mobility, help promote the balance of hole and electron transport in the light-emitting layer, and improve the efficiency performance of organic electroluminescent devices. The recombination rate of electrons and holes in the organic light-emitting layer is increased, which reduces or prevents electrons from passing through the organic light-emitting layer to the hole transport layer, thereby effectively protecting the hole transport layer material from the impact of electrons and improving the organic electricity. The lifetime of the electroluminescent device.
以上结合附图详细描述了本申请的可选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。The optional embodiments of the present application are described in detail above with reference to the accompanying drawings. However, the present application is not limited to the specific details in the above-mentioned embodiments. Within the scope of the technical concept of the present application, many simple modifications can be made to the technical solutions of the present application. All these simple variants belong to the protection scope of this application.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this application provides various possible The combination method will not be explained separately.
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。In addition, various different implementations of the present application can also be combined arbitrarily, as long as they do not violate the idea of the present application, they should also be regarded as the content disclosed in the present application.

Claims (17)

  1. 一种含氮化合物，其中，所述含氮化合物的结构式如化学式(1)所示：A nitrogen-containing compound, wherein the structural formula of the nitrogen-containing compound is shown in the chemical formula (1):
    Figure PCTCN2020122273-appb-100001
    Figure PCTCN2020122273-appb-100001
    其中，环A为成环碳原子数为10～14的稠合芳环或成环碳原子数为8～12的稠合杂芳环，且所述环A不是咔唑环；Wherein, ring A is a fused aromatic ring with 10 to 14 carbon atoms or a fused heteroaromatic ring with 8 to 12 carbon atoms, and the ring A is not a carbazole ring;
    环B为苯环、成环碳原子数为10～14的稠合芳环或成环碳原子数为8～12的稠合杂芳环；Ring B is a benzene ring, a fused aromatic ring with 10 to 14 carbon atoms, or a fused heteroaromatic ring with 8 to 12 carbon atoms;
    环C为苯环或成环碳原子数为10～14的稠合芳环；Ring C is a benzene ring or a condensed aromatic ring with 10-14 carbon atoms;
    R 1、R 2、R 3、R 4彼此相同或不同，且分别独立地选自氘、卤素基团、氰基、碳原子数为1～12的卤代烷基、碳原子数为1～12的烷基、碳原子数为2～10的烯基、碳原子数为2～10的炔基、碳原子数为3～12的环烷基、碳原子数为2～10的杂环烷基、碳原子数为1～12的烷氧基、碳原子数为1～12的烷硫基、碳原子数为3～12的三烷基硅基、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基、碳原子数为6～20的芳氧基、碳原子数为6～20的芳硫基、碳原子数为6～18的芳基甲硅烷基； R 1 , R 2 , R 3 , and R 4 are the same or different from each other and are each independently selected from deuterium, halogen group, cyano group, halogenated alkyl group having 1 to 12 carbon atoms, and one having 1 to 12 carbon atoms Alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, heterocycloalkyl groups having 2 to 10 carbon atoms, Alkoxy groups having 1 to 12 carbon atoms, alkylthio groups having 1 to 12 carbon atoms, trialkylsilyl groups having 3 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, carbon A heteroaryl group having 3 to 20 atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and an arylsilyl group having 6 to 18 carbon atoms;
    n 1表示取代基R 1的个数，n 2表示取代基R 2的个数，n 3表示取代基R 3的个数，n 4表示取代基R 4的个数，n 1、n 2、n 3、n 4彼此相同或者不同，且分别独立地选自0、1、2、3或4； n 1 represents the number of substituents R 1 , n 2 represents the number of substituents R 2 , n 3 represents the number of substituents R 3 , n 4 represents the number of substituents R 4 , n 1 , n 2 , n 3 and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4;
    当n 1大于1时，任意两个所述R 1相同或者不同，当n 2大于1时，任意两个所述R 2相同或者不同，当n 3大于1时，任意两个所述R 3相同或者不同，当n 4大于1时，任意两个所述R 4相同或者不同； When n 1 is greater than 1, any two of R 1 are the same or different, when n 2 is greater than 1, any two of R 2 are the same or different, and when n 3 is greater than 1, any two of R 3 Same or different, when n 4 is greater than 1, any two of the R 4 are the same or different;
    W选自碳原子数为6～40的取代或者未取代的芳基、碳原子数为3～40的取代或者未取代的杂芳基；W is selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms;
    W中的取代基彼此相同或不同，各自独立地选自如下基团所组成的组：氘，卤素基团，氰基，碳原子数为1～12的烷基，碳原子数为1～12的卤代烷基，碳原子数为3～10的环烷基，碳原子数为2～10的杂环烷基，碳原子数为7～10的芳烷基，碳原子数为4～10的杂芳烷基，任选地被0、1、2或3个选自氘、氟、氯、溴、氰基、烷基的取代基所取代的碳原子数为6～30的芳基，任选地被0、1、2或3个选自氘、氟、氯、溴、氰基、烷基的取代基所取代的碳原子数为3～30的杂芳基，碳原子数为1～12的烷氧基，碳原子数为1～12的烷硫基，碳原子数为3～12的三烷基硅烷基、碳原子数为6～30的芳基甲硅烷基，碳原子数为6～20的芳氧基，碳原子数为6～20的芳硫基；The substituents in W are the same or different, and are independently selected from the group consisting of deuterium, halogen group, cyano group, alkyl group with 1-12 carbon atoms, and 1-12 carbon atoms. The halogenated alkyl group, the cycloalkyl group with 3 to 10 carbon atoms, the heterocycloalkyl group with 2 to 10 carbon atoms, the aralkyl group with 7 to 10 carbon atoms, the heterocyclic alkyl group with 4 to 10 carbon atoms Aralkyl, optionally substituted by 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl, aryl groups having 6 to 30 carbon atoms, optionally Heteroaryl groups having 3 to 30 carbon atoms and 1 to 12 carbon atoms substituted with 0, 1, 2 or 3 substituents selected from deuterium, fluorine, chlorine, bromine, cyano, and alkyl The alkoxy group, an alkylthio group having 1 to 12 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and 6 carbon atoms ～20 aryloxy group, arylthio group with 6 to 20 carbon atoms;
    在所述W中，当同一原子上具有两个取代基时，任选地，连接于同一原子上的两个取代基之间相互连接以与它们共同连接的原子形成饱和或不饱和的5～18元脂肪族环或5～18元芳香环。In the W, when there are two substituents on the same atom, optionally, the two substituents connected to the same atom are connected to each other to form a saturated or unsaturated 5~ 18-membered aliphatic ring or 5-18-membered aromatic ring.
  2. 根据权利要求1所述的含氮化合物，其中，所述环A为萘环、蒽环、菲环、二苯并呋喃环、二苯并噻吩环、噻蒽环、吩噁噻环、二苯并二噁英环、10H-吩噻嗪或10H-吩噁嗪；所述环B为苯环、萘环、喹啉环或异喹啉环；所述环C为苯环、萘环、蒽环或菲环。The nitrogen-containing compound according to claim 1, wherein the ring A is a naphthalene ring, an anthracene ring, a phenanthrene ring, a dibenzofuran ring, a dibenzothiophene ring, a thianthracene ring, a phenoxathi ring, or a diphenyl ring. Dioxin ring, 10H-phenothiazine or 10H-phenoxazine; said ring B is benzene ring, naphthalene ring, quinoline ring or isoquinoline ring; said ring C is benzene ring, naphthalene ring, anthracene Ring or Philippine ring.
  3. 根据权利要求1或2所述的含氮化合物，其中，所述含氮化合物的结构式如化学式(f-1)～(f-16)中的任意一种所示：The nitrogen-containing compound according to claim 1 or 2, wherein the structural formula of the nitrogen-containing compound is shown in any one of the chemical formulas (f-1) to (f-16):
    Figure PCTCN2020122273-appb-100002
    Figure PCTCN2020122273-appb-100002
    Figure PCTCN2020122273-appb-100003
    Figure PCTCN2020122273-appb-100003
  4. 根据权利要求1～3中任意一项所述的含氮化合物，其中，所述式(1)中的
    Figure PCTCN2020122273-appb-100004
    选自以下结构：     The nitrogen-containing compound according to any one of claims 1 to 3, wherein the formula (1)
    Figure PCTCN2020122273-appb-100004
    Selected from the following structures:
    Figure PCTCN2020122273-appb-100005
    Figure PCTCN2020122273-appb-100005
  5. 根据权利要求1～4中任意一项所述的含氮化合物，其中，W为
    Figure PCTCN2020122273-appb-100006
    其中，L各自独立地选自单键、碳原子数3-30的取代或未取代的亚杂芳基、碳原子数为6-30的取代或未取代的亚芳基；Ar选自碳原子数为3-30的取代或未取代的杂芳基、碳原子数为6-30的取代或未取代的芳基；     The nitrogen-containing compound according to any one of claims 1 to 4, wherein W is
    Figure PCTCN2020122273-appb-100006
    Wherein, L is each independently selected from a single bond, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Ar is selected from a carbon atom A substituted or unsubstituted heteroaryl group with 3-30, a substituted or unsubstituted aryl group with 6-30 carbon atoms;
    所述L和Ar中的取代基为一个或多个，Ar和L中的各取代基彼此相同或不同，且各自独立地选自氘、卤素基团、氰基、碳原子数为6～20的芳基、碳原子数为3～20的取代或未取代的杂芳基、碳原子数为1～12的卤代烷基、碳原子数为1～12的烷基、碳原子数为3～12的环烷基、碳原子数为1～12的烷氧基、碳原子数为1～12的烷硫基、碳原子数为3～12的三烷基硅基、碳原子数为6～20的芳氧基、碳原子数为6～20的芳硫基和碳原子数为6～18的芳基甲硅烷基；The substituents in L and Ar are one or more, and the substituents in Ar and L are the same or different from each other, and are each independently selected from deuterium, halogen group, cyano group, and the number of carbon atoms is 6-20 Aryl groups, substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms, haloalkyl groups having 1 to 12 carbon atoms, alkyl groups having 1 to 12 carbon atoms, and 3 to 12 carbon atoms A cycloalkyl group, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a carbon number of 6 to 20 The aryloxy group, the arylthio group with 6 to 20 carbon atoms, and the arylsilyl group with 6 to 18 carbon atoms;
    当同一原子上具有两个取代基时，任选地，连接于同一原子上的两个取代基之间能够相互连接以与它们共同连接的原子形成饱和或不饱和的5～13元脂肪族环或5～13元芳香环。When there are two substituents on the same atom, optionally, the two substituents connected to the same atom can be connected to each other to form a saturated or unsaturated 5- to 13-membered aliphatic ring with the atoms connected to them. Or 5-13 membered aromatic ring.
  6. 根据权利要求5所述的含氮化合物，其中，L选自单键、碳原子为6～25的取代或未取代的亚芳基、碳原子数5～14的取代或未取代的亚杂芳基。The nitrogen-containing compound according to claim 5, wherein L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroarylene group having 5 to 14 carbon atoms. base.
  7. 根据权利要求5或6所述的含氮化合物，其中，L选自单键、或者选自化学式j-1至化学式j-13所示的基团所组成的组：The nitrogen-containing compound according to claim 5 or 6, wherein L is selected from a single bond or a group consisting of groups represented by chemical formula j-1 to chemical formula j-13:
    Figure PCTCN2020122273-appb-100007
    Figure PCTCN2020122273-appb-100007
    其中，M 2选自单键或者
    Figure PCTCN2020122273-appb-100008
    Among them, M 2 is selected from a single bond or
    Figure PCTCN2020122273-appb-100008
    Q 1～Q 5各自独立地选自N或者C(J 5)，且Q 1～Q 5中至少一个选自N；当Q 1～Q 5中的两个或者两个以上选自C(J 5)时，任意两个J 5相同或者不相同； Q 1 to Q 5 are each independently selected from N or C(J 5 ), and at least one of Q 1 to Q 5 is selected from N; when two or more of Q 1 to Q 5 are selected from C(J 5 ), any two J 5 are the same or different;
    Q 6～Q 13各自独立地选自N或者C(J 6)，且Q 6～Q 13中至少一个选自N；当Q 6～Q 13中的两个或者两个以上选自C(J 6)时，任意两个J 6相同或者不相同； Q 6 to Q 13 are each independently selected from N or C(J 6 ), and at least one of Q 6 to Q 13 is selected from N; when two or more of Q 6 to Q 13 are selected from C(J 6 ), any two J 6 are the same or different;
    Q 14～Q 23各自独立地选自N、C或者C(J 7)，且Q 14～Q 23中至少一个选自N；当Q 14～Q 23中的两个或者两个以上选自C(J 7)时，任意两个J 7相同或者不相同； Q 14 to Q 23 are each independently selected from N, C or C (J 7 ), and at least one of Q 14 to Q 23 is selected from N; when two or more of Q 14 to Q 23 are selected from C (J 7 ), any two J 7s are the same or different;
    Q 24～Q 33各自独立地选自N、C或者C(J 8)，且Q 24～Q 33中至少一个选自N；当Q 24～Q 33中的两个或者两个以上选自C(J 8)时，任意两个J 8相同或者不相同； Q 24 to Q 33 are each independently selected from N, C or C (J 8 ), and at least one of Q 24 to Q 33 is selected from N; when two or more of Q 24 to Q 33 are selected from C (J 8 ), any two J 8s are the same or different;
    E 1～E 14、J 5～J 8分别独立地选自：氢、氘、卤素基团、氰基、碳原子数为3～20的杂芳基、碳原子数为6～20的芳基、碳原子数为3～9的三烷基硅基、碳原子数为8～12的芳基甲硅烷基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为2～10的杂环烷基、碳原子数为4～10的杂环烯基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基、碳原子数为6～18的芳氧基、碳原子数为6～18的芳硫基； E 1 to E 14 and J 5 to J 8 are each independently selected from: hydrogen, deuterium, halogen group, cyano group, heteroaryl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms , Trialkylsilyl groups with 3-9 carbon atoms, arylsilyl groups with 8-12 carbon atoms, alkyl groups with 1-10 carbon atoms, haloalkyl groups with 1-10 carbon atoms , C 3-10 cycloalkyl, C 2-10 heterocycloalkyl, C 4-10 heterocycloalkenyl, C 1-10 alkoxy , Alkylthio groups having 1 to 10 carbon atoms, aryloxy groups having 6 to 18 carbon atoms, and arylthio groups having 6 to 18 carbon atoms;
    e 1～e 14以e r表示，E 1～E 14以E r表示，r为变量，表示1～14的任意整数，e r表示取代基E r的数量；当r选自1、2、3、4、5、6、9、13或14时，e r选自1、2、3或者4；当r选自7或11时，e r选自1、2、3、4、5或者6；当r为12时，e r选自1、2、3、4、5、6或者7；当r选自8或10时，e r选自1、2、3、4、5、6、7或者8；当e r大于1时，任意两个E r相同或者不相同； e 1 ~ e 14 expressed in E r, E 1 ~ E 14 to E represented by r, r is a variable, represents any integer of 1 to 14, E r E r represents the number of substituents; when r is selected from 1,2, When 3, 4, 5, 6, 9, 13, or 14, e r is selected from 1, 2, 3 or 4; when r is selected from 7 or 11, e r is selected from 1, 2, 3, 4, 5 or 6; when r is 12, e r is selected from 1, 2, 3, 4, 5, 6 or 7; when r is selected from 8 or 10, e r is selected from 1, 2, 3, 4, 5, 6 , 7 or 8; when e r is greater than 1, any two E r are the same or different;
    K 3选自O、S、Se、N(E 15)、C(E 16E 17)、Si(E 18E 19)；其中，各E 15、E 16、E 17、E 18和E 19分别独立地选自：氢、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基； K 3 is selected from O, S, Se, N (E 15 ), C (E 16 E 17 ), Si (E 18 E 19 ); wherein each of E 15 , E 16 , E 17 , E 18 and E 19 are respectively Independently selected from: hydrogen, aryl groups having 6 to 20 carbon atoms, heteroaryl groups having 3 to 20 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and rings having 3 to 10 carbon atoms alkyl;
    或者，任选地，上述E 16和E 17相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环； Or, optionally, the above-mentioned E 16 and E 17 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
    或者，任选地，上述E 18和E 19相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环； Or, optionally, the above-mentioned E 18 and E 19 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
    各K 4独立地选自单键、O、S、Se、N(E 20)、C(E 21E 22)、Si(E 23E 24)；其中，各E 20、E 21、E 22、E 23、E 24分别独立地选自：氢、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基、碳原子数为1～10的烷基、碳原子数为3～10的环烷基、碳原子数为2～10的杂环烷基； Each K 4 is independently selected from a single bond, O, S, Se, N (E 20 ), C (E 21 E 22 ), Si (E 23 E 24 ); wherein, each of E 20 , E 21 , E 22 , E 23 and E 24 are each independently selected from: hydrogen, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and the number of carbon atoms It is a cycloalkyl group of 3-10, a heterocycloalkyl group of 2-10 carbon atoms;
    或者，任选地，上述E 21和E 22相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环； Or, optionally, the above-mentioned E 21 and E 22 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms they are commonly connected to;
    或者，任选地，上述E 23和E 24相互连接以与它们共同连接的原子形成5到13元脂肪族环或5到13元芳香环。 Alternatively, optionally, the above-mentioned E 23 and E 24 are connected to each other to form a 5- to 13-membered aliphatic ring or a 5- to 13-membered aromatic ring with the atoms with which they are commonly connected.
  8. 根据权利要求5～7中任意一项所述的含氮化合物，其中，所述L选自单键、未取代的L 1、取代的L 1，其中，未取代的L 1选自如下基团所组成的组： The nitrogen-containing compound according to any one of claims 5 to 7, wherein the L is selected from a single bond, an unsubstituted L 1 , and a substituted L 1 , wherein the unsubstituted L 1 is selected from the following groups Formed group:
    Figure PCTCN2020122273-appb-100009
    Figure PCTCN2020122273-appb-100009
    其中，取代的L 1为未取代的L 1被一个或者多个选自氘、氟、氯、溴、氰基、碳原子数为1～4的烷基、碳原子数为1～4的卤代烷基、碳原子数为3～9的三烷基硅基、碳原子数为3～10的环烷基、碳原子数为6～15的芳基和碳原子数为3～12的杂芳基所取代而形成的基团，且当取代的L 1上的取代基数量为多个时，任意两个取代基之间相同或者不同。 Wherein, the substituted L 1 is unsubstituted L 1 with one or more selected from deuterium, fluorine, chlorine, bromine, cyano, alkyl having 1 to 4 carbon atoms, and haloalkane having 1 to 4 carbon atoms Group, trialkylsilyl group with 3 to 9 carbon atoms, cycloalkyl group with 3 to 10 carbon atoms, aryl group with 6 to 15 carbon atoms, and heteroaryl group with 3 to 12 carbon atoms The group formed by substitution, and when the number of substituents on the substituted L 1 is more than one, any two substituents are the same or different.
  9. 根据权利要求5～8中任意一项所述的含氮化合物，其中，Ar选自碳原子数为6～25的取代或者未取代的芳基、碳原子数为3～25的取代或者未取代的杂芳基；Ar中的取代基为一个或多个，彼此相同或不同，且各自独立地选自氘、氟、氯、氰基、碳原子数为6～12的芳基、碳原子数为3～18的取代或未取代的杂芳基、碳原子数为1～6的烷基、碳原子数为1～6的卤代烷基、碳原子数为1～6的烷氧基、碳原子数为1～6的烷硫基、碳原子数为5～10的环烷基、碳原子数为3～9的三烷基硅基、碳原子数为6～20的芳氧基、碳原子数为6～20的芳硫基和碳原子数为6～18的芳基甲硅烷基。The nitrogen-containing compound according to any one of claims 5 to 8, wherein Ar is selected from substituted or unsubstituted aryl groups having 6 to 25 carbon atoms, and substituted or unsubstituted carbon atoms having 3 to 25 The heteroaryl group; The substituents in Ar are one or more, the same or different from each other, and are each independently selected from deuterium, fluorine, chlorine, cyano, aryl groups with 6 to 12 carbon atoms, and the number of carbon atoms It is a 3-18 substituted or unsubstituted heteroaryl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom Alkylthio groups having 1 to 6 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, trialkylsilyl groups having 3 to 9 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, and carbon atoms An arylthio group having 6 to 20 and an arylsilyl group having 6 to 18 carbon atoms.
  10. 根据权利要求5～9中任意一项所述的含氮化合物，其中，Ar选自化学式i-1至化学式i-18所示的基团所组成的组：The nitrogen-containing compound according to any one of claims 5-9, wherein Ar is selected from the group consisting of groups represented by chemical formula i-1 to chemical formula i-18:
    Figure PCTCN2020122273-appb-100010
    Figure PCTCN2020122273-appb-100010
    Figure PCTCN2020122273-appb-100011
    Figure PCTCN2020122273-appb-100011
    其中，M 1选自单键或者
    Figure PCTCN2020122273-appb-100012
    Among them, M 1 is selected from a single bond or
    Figure PCTCN2020122273-appb-100012
    G 1～G 5各自独立地选自N或者C(F 1)，且G 1～G 5中至少一个选自N；当G 1～G 5中的两个以上选自C(F 1)时，任意两个F 1相同或者不相同； G 1 to G 5 are each independently selected from N or C(F 1 ), and at least one of G 1 to G 5 is selected from N; when two or more of G 1 to G 5 are selected from C(F 1 ) , Any two F 1 are the same or different;
    G 6～G 13各自独立地选自N或者C(F 2)，且G 6～G 13中至少一个选自N；当G 6～G 13中的两个以上选自C(F 2)时，任意两个F 2相同或者不相同； G 6 to G 13 are each independently selected from N or C(F 2 ), and at least one of G 6 to G 13 is selected from N; when two or more of G 6 to G 13 are selected from C(F 2 ) , Any two F 2 are the same or different;
    G 14～G 23各自独立地选自N或者C(F 3)，且G 14～G 23中至少一个选自N；当G 14～G 23中的两个以上选自C(F 3)时，任意两个F 3相同或者不相同；或者，任选地，相邻的两个F 3相互连接形成5～10元芳环或5～10元杂芳环； G 14 to G 23 are each independently selected from N or C(F 3 ), and at least one of G 14 to G 23 is selected from N; when two or more of G 14 to G 23 are selected from C(F 3 ) , Any two F 3 are the same or different; or, optionally, two adjacent F 3 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring;
    G 24～G 33各自独立地选自N或者C(F 4)，且G 24～G 33中至少一个选自N；当G 24～G 33中的两个以上选自C(F 4)时，任意两个F 4相同或者不相同；或者，任选地，相邻的两个F 4相互连接形成5～10元芳环或5～10元杂芳环； G 24 to G 33 are each independently selected from N or C(F 4 ), and at least one of G 24 to G 33 is selected from N; when two or more of G 24 to G 33 are selected from C(F 4 ) , Any two F 4 are the same or different; or, optionally, two adjacent F 4 are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring;
    G 34～G 37各自独立地选自N或者C(F 5)，当G 34～G 37中的两个以上选自C(F 5)时，任意两个F 5相同 或者不相同；或者，任选地，相邻的两个F 5相互连接形成5～10元芳环或5～10元杂芳环； G 34 to G 37 are each independently selected from N or C(F 5 ), and when two or more of G 34 to G 37 are selected from C(F 5 ), any two F 5s are the same or different; or, Optionally, two adjacent F 5s are connected to each other to form a 5- to 10-membered aromatic ring or a 5- to 10-membered heteroaromatic ring;
    G 38～G 45各自独立地选自N或者C(F 6)，且G 38～G 45中至少一个选自N；当G 38～G 45中的两个以上选自C(F 6)时，任意两个F 6相同或者不相同； G 38 to G 45 are each independently selected from N or C(F 6 ), and at least one of G 38 to G 45 is selected from N; when two or more of G 38 to G 45 are selected from C(F 6 ) , Any two F 6 are the same or different;
    G 46～G 53各自独立地选自N或者C(F 7)，且G 46～G 53中至少一个选自N；当G 46～G 53中的两个或者两个以上选自C(F 7)时，任意两个F 7相同或者不相同；或者，任选地，相邻的两个F 7相互连接形成5～10元芳环或5～10元杂芳环； G 46 to G 53 are each independently selected from N or C(F 7 ), and at least one of G 46 to G 53 is selected from N; when two or more of G 46 to G 53 are selected from C(F 7 ), any two F 7s are the same or different; or, optionally, two adjacent F 7s are connected to each other to form a 5-10 membered aromatic ring or a 5-10 membered heteroaromatic ring;
    D 1选自氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基； D 1 is selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, alkyl groups having 1 to 10 carbon atoms, and those having 1 to 10 carbon atoms A halogenated alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms;
    D 2～D 9、D 21各自独立地选自：氢、氘、氟、氯、溴、氰基、碳原子数为3～12的三烷基硅基、碳原子数为1～10的烷基、碳原子数为1～10的卤代烷基、碳原子数为3～10的环烷基、碳原子数为1～10的烷氧基、碳原子数为1～10的烷硫基、碳原子数为1～10的烷硫基、碳原子数为3～18的杂芳基； D 2 to D 9 and D 21 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl having 3 to 12 carbon atoms, and alkane having 1 to 10 carbon atoms Group, halogenated alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 3 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 10 carbon atoms, carbon Alkylthio groups having 1 to 10 atoms, heteroaryl groups having 3 to 18 carbon atoms;
    D 10～D 20、F 1～F 7各自独立地选自：氢，氘，氟，氯，溴，氰基，碳原子数为3～12的三烷基硅基，碳原子数为1～10的烷基，碳原子数为1～10的卤代烷基，碳原子数为3～10的环烷基，碳原子数为1～10的烷氧基，碳原子数为1～10的烷硫基，任选地被0、1、2或3个选自氘、氟、氯、氰基、碳原子数为1～6的烷基、碳原子数为1～6的烷氧基、碳原子数为1～6的烷胺基、碳原子数为3～7的环烷基、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为1～4的烷氧基、碳原子数为1～4的卤代烷基、碳原子数为3～9的烷基硅烷基的取代基所取代的碳原子数为6～18的芳基、碳原子数为3～18的杂芳基； D 10 to D 20 and F 1 to F 7 are each independently selected from: hydrogen, deuterium, fluorine, chlorine, bromine, cyano, trialkylsilyl groups having 3 to 12 carbon atoms, and 1 to carbon atoms 10 alkyl groups, halogenated alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkyl sulfides with 1 to 10 carbon atoms Group, optionally with 0, 1, 2 or 3 selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, carbon atom Alkylamino group with 1 to 6, cycloalkyl with 3 to 7 carbon atoms, aryl with 6 to 15 carbon atoms, heteroaryl with 3 to 12 carbon atoms, 1 carbon atom ～4 alkoxy group, C 1-4 haloalkyl group, C 3-9 alkylsilyl group substituent substituted by C 6-18 aryl group, carbon number Heteroaryl groups of 3-18;
    d 1～d 21以d k表示，D 1～D 21以D k表示，k为变量，表示1～21的任意整数，d k表示取代基D k的个数；其中，当k选自5或者17时，d k选自1、2或者3；当k选自2、7、8、12、15、16、18或者21时，d k选自1、2、3或者4；当k选自1、3、4、6、9或者14时，d k选自1、2、3、4或者5；当k为13时，d k选自1、2、3、4、5或者6；当k选自10或者19时，d k选自1、2、3、4、5、6或者7；当k为20时，d k选自1、2、3、4、5、6、7或者8；当k为11时，d k选自1、2、3、4、5、6、7、8或9；且当d k大于1时，任意两个D k相同或者不相同； d 1 ～d 21 are represented by d k , D 1 ～D 21 are represented by D k , k is a variable, representing any integer from 1 to 21, and d k is the number of substituents D k ; wherein, when k is selected from 5 Or when 17, d k is selected from 1, 2 or 3; when k is selected from 2, 7, 8, 12, 15, 16, 18 or 21, d k is selected from 1, 2, 3 or 4; when k is selected When from 1, 3, 4, 6, 9 or 14, d k is selected from 1, 2, 3, 4 or 5; when k is 13, d k is selected from 1, 2, 3, 4, 5 or 6; When k is selected from 10 or 19, d k is selected from 1, 2, 3, 4, 5, 6 or 7; when k is 20, d k is selected from 1, 2, 3, 4, 5, 6, 7 Or 8; when k is 11, d k is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; and when d k is greater than 1, any two D k are the same or different;
    K 1和K 6分别独立地选自O、S、N(D 22)、C(D 23D 24)、Si(D 28D 29)；其中，各D 22、D 23、D 24、D 28、D 29分别独立地选自：碳原子数为6～18的芳基、碳原子数为3～18的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基； K 1 and K 6 are independently selected from O, S, N (D 22 ), C (D 23 D 24 ), Si (D 28 D 29 ); wherein, each of D 22 , D 23 , D 24 , D 28 , D 29 are independently selected from: aryl groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or 3 to 10 carbon atoms的cycloalkyl;
    或者，任选地，上述D 23和D 24相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 23 and D 24 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
    或者，任选地，上述D 28和D 29相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 28 and D 29 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
    K 2选自单键、O、S、N(D 25)、C(D 26D 27)、Si(D 30D 31)；其中，各D 25、D 26、D 27、D 30、D 31分别独立地选自：碳原子数为6～18的芳基、碳原子数为3～18的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基， K 2 is selected from single bond, O, S, N (D 25 ), C (D 26 D 27 ), Si (D 30 D 31 ); wherein, each of D 25 , D 26 , D 27 , D 30 , D 31 They are independently selected from: aryl groups having 6 to 18 carbon atoms, heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkanes having 3 to 10 carbon atoms base,
    或者，任选地，上述D 26和D 27相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 26 and D 27 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
    或者，任选地，上述D 30和D 31相互连接以与它们共同连接的原子形成5到14元脂肪族环或5到14元芳香环； Or, optionally, the above-mentioned D 30 and D 31 are connected to each other to form a 5- to 14-membered aliphatic ring or a 5- to 14-membered aromatic ring with the atoms they are commonly connected to;
    K 5选自O、S、Se、N(D 32)、C(D 33D 34)，其中，D 32、D 33和D 34各自独立地选自：碳原子数为6～18的芳基、碳原子数为3～18的杂芳基、碳原子数为1～10的烷基或碳原子数为3～10的环烷基。 K 5 is selected from O, S, Se, N(D 32 ), C(D 33 D 34 ), wherein D 32 , D 33 and D 34 are each independently selected from: an aryl group having 6 to 18 carbon atoms , Heteroaryl groups having 3 to 18 carbon atoms, alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 3 to 10 carbon atoms.
  11. 根据权利要求5～10中任意一项所述的含氮化合物，其中，Ar选自未取代的Ar 1或取代的Ar 1，其中，未取代的Ar 1选自如下基团所组成的组： The nitrogen-containing compound according to any one of claims 5 to 10, wherein Ar is selected from unsubstituted Ar 1 or substituted Ar 1 , wherein the unsubstituted Ar 1 is selected from the group consisting of the following groups:
    Figure PCTCN2020122273-appb-100013
    Figure PCTCN2020122273-appb-100013
    Figure PCTCN2020122273-appb-100014
    Figure PCTCN2020122273-appb-100014
    其中，Z 1和Z 2各自独立地选自氢、碳原子数为6～20的芳基、碳原子数为3～20的杂芳基；任意两个Z 1相同或者不相同，任意两个Z 2相同或者不相同； Wherein, Z 1 and Z 2 are each independently selected from hydrogen, an aryl group with 6 to 20 carbon atoms, and a heteroaryl group with 3 to 20 carbon atoms; any two Z 1s are the same or different, any two Z 2 is the same or different;
    其中，取代的Ar 1为未取代的Ar 1被一个或者多个选自氘、氟、氯、氰基、碳原子数为1～4的烷基、碳原子数为1～4的烷氧基、碳原子数为1～4的烷胺基、碳原子数为3～7的环烷基、碳原子数为6～14的芳基、碳原子数为3～12的杂芳基、碳原子数为1～4的烷硫基、碳原子数为1～4的卤代烷基、碳原子数为3～9的烷基硅烷基所取代而形成的基团，且当Ar 1上的取代基的数量为多个时，任意两个取代基之间相同或者不相同。 Wherein, the substituted Ar 1 is unsubstituted Ar 1 with one or more selected from deuterium, fluorine, chlorine, cyano, alkyl with 1 to 4 carbon atoms, and alkoxy with 1 to 4 carbon atoms. , Alkylamino groups with 1 to 4 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, heteroaryl groups with 3 to 12 carbon atoms, carbon atoms A group formed by the substitution of alkylthio groups having 1 to 4, haloalkyl groups having 1 to 4 carbon atoms, and alkylsilyl groups having 3 to 9 carbon atoms, and when the substituents on Ar 1 are When the number is more than one, any two substituents are the same or different.
  12. 根据权利要求11所述的含氮化合物，其中，Z 1和Z 2各自独立地选自：氢、取代或者未取代的苯基、取代或者未取代的萘基、取代或者未取代的蒽基、取代或者未取代的菲基、取代或者未取代的苝基、取代或者未取代的荧蒽基、取代或者未取代的
    Figure PCTCN2020122273-appb-100015
    基、取代或者未取代的联苯基、取代或者未取代的三联苯基、取代或者未取代的芴基、取代或者未取代的二苯并噻吩基、取代或者未取代的二苯并呋喃基、取代或者未取代的N-苯基咔唑基、取代或者未取代的咔唑-9-基苯基、取代或者未取代的吡啶基、取代或者未取代的嘧啶基、取代或者未取代的吡嗪基、取代或者未取代的喹啉基、取代或者未取代的异喹啉基、取代或者未取代的喹唑啉基、取代或者未取代的苯并噁嗪、取代或者未取代的三亚苯基；     The nitrogen-containing compound according to claim 11, wherein Z 1 and Z 2 are each independently selected from: hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, Substituted or unsubstituted phenanthryl, substituted or unsubstituted perylene, substituted or unsubstituted fluoranthene, substituted or unsubstituted
    Figure PCTCN2020122273-appb-100015
    Group, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, Substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted carbazol-9-ylphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazine Group, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted benzoxazine, substituted or unsubstituted triphenylene;
    Z 1和Z 2中的取代基各自独立地选自：氟、氘、氰基、三氟甲基、三甲基硅烷基、甲基、乙基、异丙基、叔丁基、甲氧基、乙氧基、异丙氧基、三氟甲基、环戊烷基、环己烷基、苯基、联苯基、萘基、吡啶基、嘧啶基、喹啉基、异喹啉基和咔唑基。 The substituents in Z 1 and Z 2 are each independently selected from: fluorine, deuterium, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy , Ethoxy, isopropoxy, trifluoromethyl, cyclopentyl, cyclohexane, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, quinolyl, isoquinolyl and Carbazolyl.
  13. 根据权利要求1～12中任意一项所述的含氮化合物，其中，R 1、R 2、R 3、R 4彼此相同或不同，且分别独立地选自氘、卤素基团、氰基、碳原子数为1～4的卤代烷基、碳原子数为1～4的烷基、碳原子数为2～6的烯基、碳原子数为2～6的炔基、碳原子数为5～10的环烷基、碳原子数为4～6的杂环烷基、碳原子数为1～4的烷氧基、碳原子数为1～4的烷硫基、碳原子数为3～9的三烷基硅基、碳原子数为6～15的芳基、碳原子数为3～12的杂芳基、碳原子数为6～15的芳氧基、碳原子数为6～15的芳硫基、三苯基甲硅烷基；n 1、n 2、n 3、n 4彼此相同或者不同，且分别独立地选自0、1、2、3或4。 The nitrogen-containing compound according to any one of claims 1 to 12, wherein R 1 , R 2 , R 3 , and R 4 are the same or different from each other, and are each independently selected from deuterium, halogen group, cyano group, C1-C4 haloalkyl group, C1-C4 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C5-C5 10 cycloalkyl, carbon 4-6 heterocycloalkyl, carbon 1-4 alkoxy, carbon 1-4 alkylthio, carbon 3-9 The trialkylsilyl group, the aryl group with 6 to 15 carbon atoms, the heteroaryl group with 3 to 12 carbon atoms, the aryloxy group with 6 to 15 carbon atoms, the aryl group with 6 to 15 carbon atoms Arylthio, triphenylsilyl; n 1 , n 2 , n 3 , and n 4 are the same or different from each other, and are independently selected from 0, 1, 2, 3, or 4, respectively.
  14. 根据权利要求1～13中任意一项所述的含氮化合物，其中，所述含氮化合物选自如下化合物所组成的组：The nitrogen-containing compound according to any one of claims 1 to 13, wherein the nitrogen-containing compound is selected from the group consisting of the following compounds:
    Figure PCTCN2020122273-appb-100016
    Figure PCTCN2020122273-appb-100016
    Figure PCTCN2020122273-appb-100017
    Figure PCTCN2020122273-appb-100017
    Figure PCTCN2020122273-appb-100018
    Figure PCTCN2020122273-appb-100018
    Figure PCTCN2020122273-appb-100019
    Figure PCTCN2020122273-appb-100019
    Figure PCTCN2020122273-appb-100020
    Figure PCTCN2020122273-appb-100020
    Figure PCTCN2020122273-appb-100021
    Figure PCTCN2020122273-appb-100021
    Figure PCTCN2020122273-appb-100022
    Figure PCTCN2020122273-appb-100022
  15. 一种有机电致发光器件，其中，包括相对设置的阳极和阴极，以及设置于所述阳极和所述阴极之间的功能层；An organic electroluminescence device, which comprises an anode and a cathode arranged oppositely, and a functional layer arranged between the anode and the cathode;
    所述功能层包含权利要求1～14中任意一项所述的含氮化合物。The functional layer contains the nitrogen-containing compound according to any one of claims 1-14.
  16. 根据权利要求15所述的有机电致发光器件，其中，所述功能层包括空穴注入层、空穴传输层、有机发光层、电子传输层以及电子注入层，所述有机发光层含有权利要求1～14中任一项所述的含氮化合物。The organic electroluminescent device according to claim 15, wherein the functional layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer, and the organic light emitting layer contains the claims The nitrogen-containing compound according to any one of 1 to 14.
  17. 一种电子装置，其中，该电子装置包括权利要求15或16所述的有机电致发光器件。An electronic device, wherein the electronic device comprises the organic electroluminescent device according to claim 15 or 16.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114122288A (en) * 2021-11-12 2022-03-01 长春海谱润斯科技股份有限公司 Organic electroluminescent device comprising light extraction layer
WO2024045747A1 (en) * 2022-09-01 2024-03-07 陕西莱特光电材料股份有限公司 Organic compound, electronic component, and electronic device

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111848501B (en) 2020-05-08 2021-06-01 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, and electronic element and electronic device using same
CN112142548B (en) * 2020-09-30 2021-09-24 陕西莱特光电材料股份有限公司 Organic compound, and electronic element and electronic device using same
CN112480011B (en) * 2020-12-04 2022-09-13 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, organic electroluminescent device, and electronic device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110615759A (en) * 2019-09-25 2019-12-27 陕西莱特光电材料股份有限公司 Compound, photoelectric conversion device, and electronic device
WO2020045924A1 (en) * 2018-08-29 2020-03-05 주식회사 엘지화학 Novel compound and organic light emitting diode using same
WO2020046049A1 (en) * 2018-08-31 2020-03-05 주식회사 엘지화학 Novel compound and organic light emitting device using same
CN111018797A (en) * 2019-12-26 2020-04-17 陕西莱特光电材料股份有限公司 Organic compound, electronic element containing the same, and electronic device
CN111454197A (en) * 2019-12-31 2020-07-28 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, organic electroluminescent device, and electronic device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020045924A1 (en) * 2018-08-29 2020-03-05 주식회사 엘지화학 Novel compound and organic light emitting diode using same
WO2020046049A1 (en) * 2018-08-31 2020-03-05 주식회사 엘지화학 Novel compound and organic light emitting device using same
CN110615759A (en) * 2019-09-25 2019-12-27 陕西莱特光电材料股份有限公司 Compound, photoelectric conversion device, and electronic device
CN111018797A (en) * 2019-12-26 2020-04-17 陕西莱特光电材料股份有限公司 Organic compound, electronic element containing the same, and electronic device
CN111454197A (en) * 2019-12-31 2020-07-28 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, organic electroluminescent device, and electronic device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114122288A (en) * 2021-11-12 2022-03-01 长春海谱润斯科技股份有限公司 Organic electroluminescent device comprising light extraction layer
WO2024045747A1 (en) * 2022-09-01 2024-03-07 陕西莱特光电材料股份有限公司 Organic compound, electronic component, and electronic device

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