CN116209291A - Application of carbazole derivative in organic electroluminescent device cover layer - Google Patents
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- CN116209291A CN116209291A CN202310063764.4A CN202310063764A CN116209291A CN 116209291 A CN116209291 A CN 116209291A CN 202310063764 A CN202310063764 A CN 202310063764A CN 116209291 A CN116209291 A CN 116209291A
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Abstract
The invention provides application of carbazole derivative in a covering layer of an organic electroluminescent device, and relates to the technical field of organic electroluminescent. In order to improve the light extraction efficiency of the organic electroluminescent device, the invention provides the carbazole derivative applied to the cover layer of the organic electroluminescent device, which has higher polarization rate due to stronger electron withdrawing capability and a larger conjugated system, so that the carbazole derivative has higher refractive index, can reduce total reflection generated when the device emits light, inhibit extinction reaction caused by surface plasma movement, and effectively improve the light extraction efficiency of the organic electroluminescent device, thereby improving the luminous efficiency of the device. Meanwhile, the carbazole derivative has higher glass transition temperature, good thermal stability of the material, good film forming property and thermal stability, and can isolate moisture and oxygen, avoid damage to internal materials of the organic electroluminescent device and prolong the service life of the device.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to application of a carbazole derivative in a covering layer of an organic electroluminescent device.
Background
The organic electroluminescent device is a self-luminous display device and has the characteristics of wide viewing angle, low driving voltage, high luminous efficiency and the like. The device is characterized by light weight, flexibility and simple manufacturing process, and can be widely applied to the fields of mobile phones, televisions, wearing, illumination and the like, so that the organic electroluminescent device becomes a research hot spot.
The organic electroluminescent device is generally a classical sandwich structure composed of a cathode, an anode and an organic functional layer, wherein the organic functional layer mainly comprises: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL) and an Electron Injection Layer (EIL). Indium Tin Oxide (ITO) is typically used as the anode of the device and low work function metals are used as the cathode of the device. Electrons and holes are injected into the organic layer from the cathode and the anode, respectively, and migrate in the organic layer under the driving of an applied voltage, and then the electrons and holes are recombined in the light emitting layer to generate excitons, and the excitons are transferred back to the ground state by radiation and emit light. Currently, the research and development direction of the organic electroluminescent device focuses on how to increase the internal quantum efficiency, that is, how to increase the effective injection and transmission balance of carriers to increase the luminous efficiency, and ignoring the huge gap between the external quantum efficiency and the internal quantum efficiency is a key to restrict the development of the OLED. Light close to 80% cannot be emitted, heat is limited in the organic electroluminescent device to be dissipated, and excessive heat accumulation can affect the service life of other organic materials in the device, such as organic material deterioration, unbalanced carrier transmission, and efficiency roll-off of the organic electroluminescent device caused by a large amount of water and oxygen.
In order to solve the problem that no light approaching 80% can be emitted, a top emission device is provided, a transmission electrode is arranged above an organic light emitting layer, a reflection electrode is arranged below the organic light emitting layer, and light rays are emitted from the opposite direction of a substrate, so that the light ray transmission area is increased, and the light approaching 80% is prevented from being concentrated in the device. In order to improve the light extraction efficiency, a covering layer is added on the transparent electrode of the top emission device to serve as a light extraction functional layer, so that the optical interference distance is adjusted, the external light reflection is restrained, and the extinction reaction caused by surface plasma movement is restrained.
Disclosure of Invention
In view of the foregoing problems of the prior art, the present invention provides a use of a carbazole derivative in a capping layer of an organic electroluminescent device, the carbazole derivative being represented by the following formula I:
ar is selected from any one of the following structures in formula 2 or formula 3:
the X is 1 Independently selected from C (R) 2 ) Or N, said X is independently selected from C (R 3 ) Or N, said X 2 Selected from O, S, C (R) 4 R 5 ) Or N (R) 6 )；
And L is equal to 3 X bonded to Ar is selected from C; and L is equal to 3 Bonded X 1 Selected from C and L 2 Bonded X 1 Selected from C;
the R is 1 、R 2 、R 3 Independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said n 1 Selected from 0, 1 or 2;
having two or more R' s 2 When present, two or more R' s 2 Identical or different from each other, or adjacent two R' s 2 Can be connected to form a substituted or unsubstituted ring, and there are twoOr a plurality of R 3 When present, two or more R' s 3 Identical or different from each other, or adjacent two R' s 3 Can be connected to form any one of a substituted or unsubstituted benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring or a C3-C7 aliphatic ring;
the R is 4 、R 5 、R 6 Independently selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or R is 4 、R 5 Can be linked to form a substituted or unsubstituted ring;
the L is 1 Independently selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, and substituted or unsubstituted C2-C30 heteroarylene;
the L is 2 、L 3 Independently selected from any one or more of single bond, substituted or unsubstituted following groups: phenylene, biphenylene, terphenyl, naphthylene, anthrylene, phenanthrylene, triphenylene, benzocyclopropylene, benzocyclobutene, benzocyclopentylene, benzocyclohexylene, pyridylene, pyrimidinylene, pyrazinylene, pyridazinylene, triazinylene, quinolinylene, isoquinolylene, quinazolinylene, quinoxalinylene, phenanthroline, naphthyridine, benzothiophenylene, benzofuranylene, dibenzothiophenylene, dibenzofuranylene, fluorenylene, carbazolylene, N-heterobenzothiophenylene, N-heterobenzofuranylene, N-heterodibenzothiophenylene, N-heterodibenzofuranylene;
the Ar is as follows 1 Independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, unsubstituted or C6-C30 aryl substituted with one or more Ra, or selected from any one of structures represented by the following formulas 4-1 to 4-8:
In the formulas 4-1 to 4-8,
z is independently selected from C (Rb) or N, and at least one Z in each group of formulas 4-1 to 4-5 is selected from N;
the Y is selected from C (Rb) or N;
the M is 1 Selected from O, S, C (RcRd) or N (Re), said M 2 Selected from C (Rc) or N, said M 3 Selected from O, S, C (RcRd) or N (Re);
the Ra is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl and substituted or unsubstituted C6-C30 aryl; when two or more Ra are present, two or more Ra may be the same or different from each other, or two Ra adjacent to each other may be linked to form a substituted or unsubstituted ring;
the Rb is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; when two or more Rb are present, two or more Rb are the same or different from each other or adjacent two Rb may be linked to form a substituted or unsubstituted ring;
The Rf is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said m is selected from 0, 1 or 2;
the Rc, rd and Re are independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atoms, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or Rc, rd form a substituted or unsubstituted ring;
the Ar is as follows 2 Independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl.
The invention also provides an organic electroluminescent device, which comprises an anode, an organic layer, a cathode and a covering layer positioned outside at least one electrode in the anode or the cathode, wherein the covering layer comprises at least one or more carbazole derivatives used for the covering layer.
Advantageous effects
The carbazole derivative applied to the cover layer has higher polarizability and higher conjugated system, so that the carbazole derivative can reduce total reflection phenomenon generated when the carbazole derivative is applied to the cover layer of an organic electroluminescent device, effectively improve light extraction efficiency of the device, and further improve luminous efficiency of the organic electroluminescent device.
Meanwhile, the carbazole derivative has higher glass transition temperature, good thermal stability of the material, capability of avoiding crystallization during vapor deposition film formation, good film forming property and thermal stability, capability of isolating moisture and oxygen, capability of avoiding damage to internal materials of the organic electroluminescent device, and prolonged service life of the device.
Detailed Description
The following description of the embodiments of the present invention will be made more complete and obvious by the following description of the embodiments of the present invention, wherein the embodiments are described in some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance.
In the context of the present description of the invention,
meaning a moiety attached to another substituent. />
May be attached at any optional position of the attached group/fragment. For example->
Representation->
And so on.
In this specification, when a substituent is not fixed in position on a ring, it is meant that it can be attached to any of the corresponding selectable positions of the ring. For example, the number of the cells to be processed,
can indicate->
And so on.
Examples of the halogen atom according to the present invention may include fluorine, chlorine, bromine and iodine.
The alkyl group according to the present invention means a monovalent group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight chain alkyl group or a branched alkyl group, preferably having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms. Specific examples may include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, and the like, but are not limited thereto.
Alkenyl in the context of the present invention means a monovalent radical obtained by removing one hydrogen atom from an olefin molecule, which may be a straight-chain alkenyl or branched alkenyl radical, preferably having from 2 to 15 carbon atoms, more preferably from 2 to 12 carbon atoms, particularly preferably from 2 to 6 carbon atoms. Specific examples may include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, styryl, and the like, but are not limited thereto.
Cycloalkyl according to the invention is a monovalent radical obtained by removing one hydrogen atom from a cyclic alkane molecule, preferably having 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms. Specific examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, etc., preferably cycloalkyl is cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, etc., but are not limited thereto.
The heterocycloalkyl group according to the present invention refers to a generic term for groups in which one or more carbon atoms in the heterocycloalkyl group are replaced by heteroatoms including, but not limited to, oxygen, sulfur, nitrogen, silicon or phosphorus atoms, preferably having 2 to 15 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 6 carbon atoms. Specific examples may include, but are not limited to, tetrahydropyrrolyl, piperidinyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, and the like.
Aryl according to the invention means a monovalent radical obtained by removing one hydrogen atom from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl, preferably having from 6 to 60 carbon atoms, more preferably from 6 to 30 carbon atoms, particularly preferably from 6 to 18 carbon atoms, most preferably from 6 to 12 carbon atoms. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, for example, phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, tetrabiphenyl, 1-phenylnaphthyl, 2-phenylnaphthyl, etc., but is not limited thereto; the condensed ring aryl group means an aryl group having two or more aromatic rings in the molecule and condensed with each other by sharing two adjacent carbon atoms, for example, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, 
A group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, benzofluorenyl group, triphenylene group, fluoranthenyl group, 9' -spirobifluorenyl group, and the like, but is not limited thereto. />
Heteroaryl according to the present invention refers to the generic term for groups in which one or more aromatic nucleus carbon atoms in the aryl group are replaced by heteroatoms including, but not limited to, oxygen, sulfur, nitrogen, silicon or phosphorus atoms, preferably having 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 18 carbon atoms, most preferably 2 to 12 carbon atoms. The attachment site of the heteroaryl group may be on a ring-forming carbon atom or on a ring-forming heteroatom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a fused ring heteroaryl group. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, etc., but is not limited thereto; the fused ring heteroaryl group includes, but is not limited to, quinolinyl, isoquinolinyl, benzoquinolinyl, benzoisoquinolinyl, quinazolinyl, quinoxalinyl, benzoquinazolinyl, benzoquinoxalinyl, phenanthroline, naphthyridinyl, indolyl, benzothiophenyl, benzofuranyl, N-heterobenzothiophenyl, N-heterobenzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, N-heterodibenzofuranyl, dibenzofuranyl, dibenzothiophenyl, N-heterodibenzothiophenyl, benzodibenzothiophenyl, dibenzoxazolyl, dibenzoimidazolyl, dibenzothiazolyl, carbazolyl, N-heterocarbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiazinyl, spirofluorene oxaanthracenyl, spirofluorene thioanthracenyl, and the like.
The aliphatic ring according to the present invention is a cyclic hydrocarbon having aliphatic properties, and the molecule contains a closed carbon ring, preferably 3 to 60 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms, and most preferably 3 to 7 carbon atoms. Which may form a mono-or polycyclic hydrocarbon, may be fully unsaturated or partially unsaturated, and specific examples may include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like, but are not limited thereto.
Arylene as used herein refers to an aryl group having 2 binding sites, i.e., a divalent group. These are not only divalent groups but also aryl groups as described above.
Heteroaryl ene in the sense of the present invention means that there are 2 binding sites, i.e. divalent groups, on the heteroaryl group. They may be applied to the above description of heteroaryl groups, in addition to the divalent groups, respectively.
"substituted … …" as used herein, such as "substituted alkyl, substituted alkenyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene" refers to an independent mono-or poly-substitution with: deuterium, tritium, cyano, nitro, hydroxyl, halogen atom, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C1-C12 alkylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylamino, and the like, but are not limited thereto, and when two or more substituents are present, adjacent substituents may be linked to form a ring. Preferably mono-or polysubstituted by: deuterium, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, deuteromethyl, ethyl, isopropyl, t-butyl, deuterated t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, deuterophenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, anthracenyl, phenanthryl, triphenylene, perylenyl, pyrenyl, benzyl, t-butyl substituted phenyl, adamantyl substituted phenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, diphenylamino, pyridyl, pyrimidinyl, triazinyl, carbazolyl, acridinyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothiophenyl, phenoxazinyl, and the like, but not limited thereto.
The term "link-forming ring" as used herein means that two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:
in the present invention, the ring formed by the connection may be an aromatic ring system, an aliphatic ring system or a ring system formed by the fusion of both, and the ring formed by the connection may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a spiro ring or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentaacene, cyclohexene, cyclohexane acene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.
"Spiro" as used herein refers to structures in which two carbocycles share one carbon atom, and preferably have 15 to 60 carbon atoms, more preferably 15 to 30 carbon atoms. In particular, the spiro structure may include any of the substituted or unsubstituted groups of the following structural formula:
for example, when the spiro structure is combined with fluorene, any of the substituted or unsubstituted groups of the following structural formula may be formed:
the invention provides application of a carbazole derivative in a covering layer of an organic electroluminescent device, wherein the carbazole derivative is represented by the following formula I:
Ar is selected from any one of the following structures in formula 2 or formula 3:
the X is 1 Independently selected from C (R) 2 ) Or N, said X is independently selected from C (R 3 ) Or N, said X 2 Selected from O, S, C (R) 4 R 5 ) Or N (R) 6 )；
And L is equal to 3 X bonded to Ar is selected from CH; and L is equal to 3 Bonded X 1 Selected from CH, and L 2 Bonded X 1 Selected from CH;
the R is 1 、R 2 、R 3 Independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said n 1 Selected from 0, 1 or 2;
having two or more R' s 2 When present, two or more R' s 2 Identical or different from each other, or adjacent two R' s 2 Can be linked to form a substituted or unsubstituted ring, with two or more R' s 3 When present, two or more R' s 3 Identical or different from each other, or adjacent two R' s 3 Can be connected to form any one of a substituted or unsubstituted benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring or a C3-C7 aliphatic ring;
The R is 4 、R 5 、R 6 Independently selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or R is 4 、R 5 Can be linked to form a substituted or unsubstituted ring;
the L is 1 Independently selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, and substituted or unsubstituted C2-C30 heteroarylene;
the L is 2 、L 3 Independently selected from any one or more of single bond, substituted or unsubstituted following groups: phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, triphenylene, and benzocyclopropeneA group, a benzocyclobutene group, a benzocyclopentylene group, a benzocyclohexylene group, a pyridylene group, a pyrimidinylene group, a pyrazinylene group, a pyridazinylene group, a triazinylene group, a quinolinylene group, an isoquinolylene group, a quinazolinylene group, a quinoxalinylene group, a phenanthroline group, a naphthyridine group, a benzothienyl group, a benzofuranylene group, a dibenzothiophenylene group, a dibenzofuranylene group, a fluorenylene group, a carbazole group, an N-heterobenzothiophenyl group, an N-heterobenzofuranyl group, an N-heterodibenzothiophenyl group;
The Ar is as follows 1 Independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, unsubstituted or C6-C30 aryl substituted with one or more Ra, or selected from any one of structures represented by the following formulas 4-1 to 4-8:
in the formulas 4-1 to 4-8,
z is independently selected from C (Rb) or N, and at least one Z in each group of formulas 4-1 to 4-5 is selected from N;
the Y is selected from C (Rb) or N;
the M is 1 Selected from O, S, C (RcRd) or N (Re), said M 2 Selected from C (Rc) or N, said M 3 Selected from O, S, C (RcRd) or N (Re);
the Ra is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl and substituted or unsubstituted C6-C30 aryl; when two or more Ra are present, two or more Ra may be the same or different from each other, or two Ra adjacent to each other may be linked to form a substituted or unsubstituted ring;
the Rb is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; when two or more Rb are present, two or more Rb are the same or different from each other or adjacent two Rb may be linked to form a substituted or unsubstituted ring;
The Rf is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said m is selected from 0, 1 or 2;
the Rc, rd and Re are independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atoms, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or Rc, rd form a substituted or unsubstituted ring;
the Ar is as follows 2 Independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl.
Preferably, the carbazole derivative is selected from the structures represented by the following formula I-1 or formula I-2:
preferably, the Ar 1 Selected from any one of substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, or selected from structures represented by formulas 4-1 to 4-8, or selected from any one of the following groups:
said E is selected from C3-C7 aliphatic rings which are unsubstituted or substituted by one or more Ra,
the Ra is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl and substituted or unsubstituted C6-C30 aryl; when two or more Ra are present, two or more Ra may be the same or different from each other, or two Ra adjacent to each other may be linked to form a substituted or unsubstituted ring;
the m is 1 Independently selected from 0, 1, 2, 3, 4 or 5, said m 2 Independently selected from 0, 1, 2, 3 or 4, said m 3 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, said m 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said m 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11;
preferably, the Ar 1 Selected from the structures represented by formulas 4-6 or 4-8:
still preferably, the formulas 4 to 6 are selected from any one of the following groups:
the formula 4-8 is selected from any one of the following groups:
the Rb is selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen atom, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexenyl, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthracenyl, phenanthryl, triphenylene, fluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, carbazolyl, deuteromethyl, deuteroethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornane, deuterated norbornyl deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylenyl, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thienyl, deuterated benzothienyl, deuterated dibenzothienyl, deuterated carbazolyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, adamantyl-substituted phenyl, adamantyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, any one of deuterated isopropyl substituted phenyl and deuterated tertiary butyl substituted phenyl or any one of five-membered aliphatic ring, six-membered aliphatic ring, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring can be formed by connecting two adjacent Rb;
The m is 1 Independently selected from 0, 1, 2, 3, 4 or 5, said m 2 Independently selected from 0, 1, 2, 3 or 4, said m 3 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, said m 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said m 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said m 7 Independently selected from 0, 1, 2 or 3, said m 8 Selected from 0, 1 or 2, said m 9 Independently selected from 0, 1, 2, 3, 4, 5 or 6, said m 10 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.
Preferably, the Ar 1 Selected from any one of the following groups:
the Ra is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl;
or two adjacent Ra can be connected to form any one of five-membered aliphatic ring, six-membered aliphatic ring, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring.
Still preferably, the Ar 1 Methyl, ethyl, n-propyl, isopropyl which are unsubstituted or substituted by any one or more substituents selected from the group consisting of "deuterium, tritium, cyano, halogen atom, C1-C6 alkyl Any one of a group, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropanyl, cyclobutyl, cyclopentanyl, cyclohexenyl, cycloheptyl, adamantyl, norbornyl, or any one of the following groups:
the m is 1 Independently selected from 0, 1, 2, 3, 4 or 5, said m 2 Independently selected from 0, 1, 2, 3 or 4, said m 3 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, said m 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said m 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said m 6 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, said m 7 Independently selected from 0, 1, 2 or 3, said m 8 Selected from 0, 1 or 2, said m 9 Independently selected from 0, 1, 2, 3, 4, 5 or 6, said m 10 Independently selected from0. 1, 2, 3, 4, 5, 6, 7 or 8.
Preferably, the method comprises the steps of, the Ra is independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, hydroxy, halogen atom, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutyl, cyclopentylalkyl, cycloheptane, adamantyl, norbornane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthryl, phenanthryl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, deuteromethyl, deuteroethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornane methyl substituted adamantyl, ethyl substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylyl, deuterated fluorenyl, fluoro substituted phenyl, fluoro substituted biphenyl, cyano substituted phenyl, cyano substituted biphenyl, methyl substituted phenyl, methyl substituted biphenyl, ethyl substituted phenyl, ethyl substituted biphenyl, isopropyl substituted phenyl, isopropyl substituted biphenyl, tert-butyl substituted phenyl, tert-butyl substituted biphenyl, trifluoromethyl substituted phenyl, adamantyl substituted biphenyl, norbornyl substituted phenyl, norbornyl substituted biphenyl, methyl substituted naphthyl, ethyl substituted naphthyl, isopropyl substituted naphthyl, any one of tert-butyl substituted naphthyl, deuterated methyl substituted phenyl, deuterated isopropyl substituted phenyl and deuterated tert-butyl substituted phenyl.
Preferably, the method comprises the steps of, the Rb is independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthracenyl, phenanthryl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiophenyl, and the like deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylene, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thiophenyl, deuterated benzothienyl, deuterated dibenzothiophenyl, deuterated carbazolyl, deuterated pyridinyl, deuterated pyrimidinyl, fluoro-substituted phenyl, fluoro-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, any one of ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, trifluoromethyl-substituted biphenyl, adamantyl-substituted phenyl, adamantyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl;
Preferably, the method comprises the steps of, the Rf is independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexen, benzocycloheptane, naphthyl, anthracenyl, phenanthryl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiophenyl, and the like deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylene, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thiophenyl, deuterated benzothienyl, deuterated dibenzothiophenyl, deuterated carbazolyl, deuterated pyridinyl, deuterated pyrimidinyl, fluoro-substituted phenyl, fluoro-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, any one of ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, trifluoromethyl-substituted biphenyl, adamantyl-substituted phenyl, adamantyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl.
Preferably, the Ar 2 Selected from the group consisting of hydrogen, deuterium, cyano, nitro, hydroxy, halogen atom, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane,Any one of cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, or any one of the following groups:
the R is 7 Independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R 7 Can be linked to form a substituted or unsubstituted ring;
the X is 3 Independently selected from O, S, C (R 8 R 9 ) Or N (R) 10 ) The X is 4 Independently selected from C (R) 8 ) Or N;
the R is 8 、R 9 、R 10 Independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or R is 8 、R 9 Can be linked to form a substituted or unsubstituted ring;
the a 1 Independently selected from 0, 1, 2, 3, 4 or 5, said a 2 Independently selected from 0, 1, 2, 3 or 4, said a 3 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, said a 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said a 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said a 6 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, said a 7 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said a 8 Independently selected from 0, 1, 2 or 3, said a 9 Independently selected from 0, 1Or 2, said a 10 Independently selected from 0, 1, 2, 3, 4, 5 or 6.
Still more preferably, the R 7 Independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen atom, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexenyl, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthracenyl, phenanthrene, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, deuteromethyl, thiophenyl, and the like deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylyl, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thienyl, deuterated benzothienyl, deuterated dibenzothienyl, deuterated carbazolyl, fluoro-substituted phenyl, fluoro-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, adamantyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuteromethyl-substituted phenyl, deuteroisopropyl-substituted phenyl Any one of deuterated tertiary butyl substituted phenyl.
Preferably, the said
Selected from any one of the following groups: />
The X is 2 Selected from O, S, C (R) 4 R 5 ) Or N (R) 6 )；
The R is 4 、R 5 、R 6 Independently selected from hydrogen, deuterium, tritium, cyano, nitro, hydroxy, trifluoromethyl, halogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexenyl, cycloheptane, norbornane, adamantane, deuteromethyl, deuteroethyl, deutero-n-propyl, deutero-isopropyl, deutero-tert-butyl, deutero-adamantane, deutero-norbornane, methyl-substituted adamantane, ethyl-substituted adamantane, or the following groups that are unsubstituted or substituted with one or more groups selected from the group consisting of deuterium, cyano, trifluoromethyl, halogen atom, C1-C6 alkyl, adamantane, norbornane: any one of phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexen, benzocycloheptane, naphthyl, anthryl, phenanthryl, triphenylene, fluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, carbazolyl; or R is 4 、R 5 Can be connected to form a spiro ring;
said n 3 Independently selected from 0, 1, 2, 3 or 4, said n 4 Independently selected from 0,1. 2, 3, 4, 5 or 6, said n 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said n 6 Independently selected from 0, 1, 2 or 3, said n 7 Independently selected from 0, 1 or 2, said n 8 Independently selected from 0, 1, 2, 3, 4 or 5, said n 9 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7.
Preferably, said R 1 、R 2 Independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen atom, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexenyl, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthracenyl, phenanthrene, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, deuteromethyl, thiophenyl, and the like deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylyl, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thienyl, deuterated benzothienyl, deuterated dibenzothienyl, deuterated carbazolyl, fluoro-substituted phenyl, fluoro-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, adamantyl Any one of alkyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl.
Preferably, said R 3 Independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen atom, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexenyl, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthracenyl, phenanthrene, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, deuteromethyl, thiophenyl, and the like deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylyl, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thienyl, deuterated benzothienyl, deuterated dibenzothienyl, deuterated carbazolyl, fluoro-substituted phenyl, fluoro-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, adamantyl-substituted biphenyl Phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl. Or two adjacent R 3 And the benzene ring or naphthalene ring is formed by connection.
Preferably, the L 1 ～L 3 Independently selected from a single bond or any one of the following groups:
the Rx is independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, hydroxyl, halogen atom, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, deuteromethyl, deuteroethyl, deuterisopropyl, deuterated tert-butyl, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, deuterated pyridinyl, deuterated pyrimidinyl, deuterated pyridazinyl, deuterated pyrazinyl, deuterated quinolinyl, deuterated isoquinolinyl, or two adjacent Rx can be connected to form a substituted or unsubstituted benzene ring or naphthalene ring;
Said b 1 Independently selected from 0, 1, 2, 3 or 4, said b 2 Independently selected from 0, 1, 2 or 3, said b 3 Independently selected from 0, 1 or 2, said b 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said b 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
Still preferably, the L 1 ～L 3 Independently selected from a single bond or any one of the following groups:
preferably, the said
Of the four X groups of each ring, up to three are selected from N; further preferably, of the four X's per ring, at most two are selected from N; it is also preferred that, of the four X's per ring, at most one is selected from N.
Most preferably, the carbazole derivative is selected from any one of the following structures:
the carbazole derivatives of the present invention are shown in the above specific structural forms, but the present invention is not limited to the chemical structures shown in the above list, and substituents are included in the structures shown in the formula I.
The invention also provides an organic electroluminescent device, which comprises an anode, an organic layer, a cathode and a covering layer positioned outside at least one electrode in the anode or the cathode, wherein the covering layer comprises at least one or more carbazole derivatives.
Preferably, the organic electroluminescent device according to the present invention may comprise one or more organic layers, which may comprise a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, etc. The organic layer may be formed of a single-layer structure or a multilayer structure in which the above organic layers are stacked; meanwhile, each organic layer may further include one or more layers, for example, the hole transport layer includes a first hole transport layer and a second hole transport layer. However, the structure of the organic electroluminescent device is not limited thereto, and may include fewer or more organic layers.
Preferably, the cover layer is located outside the cathode, and the cover layer contains at least one or more carbazole derivatives described in the present invention.
Preferably, the cover layer may comprise one or more layers of structure; specifically, the cover layer comprises at least one layer of a first cover layer, a second cover layer and a third cover layer, and at least one layer of the first cover layer, the second cover layer or the third cover layer comprises any one or more of carbazole derivatives.
As the anode material of the present invention, a material having a high work function is preferable. The anode may be a transmissive electrode, a reflective electrode, or a semi-transmissive electrode. The material for forming the anode may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin oxide (SnO) 2 ) Zinc oxide (ZnO) or any combination thereof; it may also be selected from magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) or any combination thereof. While the anode may be of a single-layer structure or a multilayer structure comprising two or more layers, for example, the anode may be of a single-layer structure with Al or a three-layer structure of ITO/Ag/ITO, but is not limited thereto
As the hole injection layer material according to the present invention, a material that can receive holes injected from the anode at a low voltage is preferable, and any one or more of the following structures may be selected: metalloporphyrins, oligothiophenes, arylamine derivatives, perylene derivatives, hexanitrile hexaazabenzophenanthrene compounds, quinacridone compounds, anthraquinone compounds, and polyaniline-based and polythiophene-based conductive polymers, etc., but are not limited thereto.
As the hole transport layer material of the present invention, a material having a high hole mobility is preferable, and may be selected from any one or more of the following structures: carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, stilbene derivatives, phthalocyanines, hexanitrile hexaazabenzophenanthrenes, quinacridones, anthraquinones, polyanilines, polythiophenes, polyvinylcarbazoles, and the like, but are not limited thereto.
As the light-emitting layer material of the present invention, a red, green or blue light-emitting material may be used, and generally comprises a guest (doped) material and a host material, and the guest material may be a simple fluorescent material or phosphorescent material, or may be a combination of fluorescent and phosphorescent materials. The host material of the light-emitting layer needs to have a bipolar charge transport property and an appropriate energy level to efficiently transfer excitation energy to the guest light-emitting material, and examples thereof include distyrylaryl derivatives, stilbene derivatives, carbazole derivatives, triarylamine derivatives, anthracene derivatives, and pyrene derivatives. The guest material may be selected from any one or more of the following structures: metal complexes (e.g., iridium complexes, platinum complexes, osmium complexes, rhodium complexes, etc.), anthracene derivatives, pyrene derivatives, perylene derivatives, etc., but are not limited thereto.
As the electron transport layer material according to the present invention, a material having high electron mobility is preferable, and may be selected from any one or more of the following structures: metal chelates, oxazole derivatives, thiazole derivatives, diazole derivatives, azabenzene derivatives, diazoanthracene derivatives, silicon-containing heterocyclic compounds, boron-containing heterocyclic compounds, cyano compounds, quinoline derivatives, phenanthroline derivatives, benzimidazole derivatives, and the like, but are not limited thereto.
As the electron injection layer material of the present invention, a material having a low work function is preferable, and specific examples may include: a metal, an alkali metal, an alkaline earth metal, an alkali metal halide, an alkaline earth metal halide, an alkali metal oxide, an alkaline earth metal oxide, an alkali metal salt, an alkaline earth metal salt, a metal complex, or other substances having high electron injection properties. Examples can be cited as Li, ca, sr, liF, csF, caF 2 、BaO、Li 2 CO 3 、CaCO 3 、Li 2 C 2 O 4 、Cs 2 C 2 O 4 、CsAlF 4 LiOx, yb, tb, 8-hydroxy groupCesium quinolinolate, aluminum tris (8-hydroxyquinoline), and the like, but is not limited thereto.
As the cathode material according to the present invention, a material having a low work function is preferable, and the cathode may be selected from a transmissive electrode, a semi-reflective electrode, or a reflective electrode. When the cathode is a transmissive electrode, the material used to form the cathode may be selected from transparent metal oxides (e.g., ITO, IZO, etc.); it may also be selected from Ag, mg, cu, al, pt, pd, au, ni, nd, ir, cr, li, ca, liF/Ca, liF/Al, mo, ti, compounds including them or mixtures thereof (e.g., mixtures of Ag and Mg), but is not limited thereto.
The invention also provides a preparation method of the compound shown in the formula I, but the preparation method of the invention is not limited to the method. The core structure of the compounds of formula I may be prepared by the reaction schemes shown below, substituents may be bonded via methods known in the art, and the type and position of substituents or the number of substituents may be varied according to techniques known in the art.
[ synthetic route ]
(1) When Ar is selected from the structure of formula 2, the compound of formula I is selected from the group consisting of formula I-1, and the compound represented by formula I-1 can be prepared by the following route:
(2) When Ar is selected from the structure of formula 3, the compound of formula I is selected from the group consisting of formula I-2, and the compound represented by formula I-2 can be prepared by the following route:
(3) when-L 2 —Ar 2 When selected from hydrogen, the compounds represented by formula I-2 may be prepared by the following route:
the above-mentioned raw materials a to d may be commercially available products or may be prepared by a synthesis method commonly used in the art, and taking the raw materials b, c and d as examples, they may be prepared by the following preparation methods:
preparation of raw material b:
preparation of raw material c:
preparation of raw material b:
xa, xb, xc, xd, xe, xf, xg are independently selected from any one of Cl, br and I.
Description of the starting materials, reagents and characterization equipment:
the raw materials and reagent sources used in the following examples are not particularly limited, and may be commercially available products or prepared by methods well known to those skilled in the art.
The mass spectrum uses a Wotes G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer in UK, chloroform as a solvent;
the elemental analysis uses a Vario EL cube type organic elemental analyzer of Elementar, germany, and the mass of the sample is 5-10 mg;
Synthesis example 1 preparation of intermediate d-86
Under the protection of argon, the reaction flask was charged with raw material m-86 (14.24 g,80.00 mmol), raw material n-86 (22.95 g,80.00 mmol), K 2 CO 3 (16.58 g,120.00 mmol) and 500mL tolueneEthanol/water (2:1:1) mixed solvent, argon was substituted for air three times, and Pd (PPh) was added 3 ) 4 (0.92 g,0.80 mmol), stirring the mixture, heating the above system to reflux for reaction for 5 hours, cooling to room temperature after the reaction is finished, adding distilled water, separating to keep toluene layer, drying with anhydrous magnesium sulfate, filtering, rotationally evaporating to concentrate the solvent, cooling to crystallize, suction filtering, and then using toluene: recrystallisation from methanol=10:1 gives intermediate d-86 (18.06 g, 77% yield) with HPLC purity > 99.87%. Mass spectrum m/z:292.0754 (theory: 292.0765).
Following the procedure described above for the preparation of intermediate d-86, in accordance with synthetic example 1, the present invention also synthesizes the following intermediates:
synthesis example 2 preparation of intermediate b-361
(1) Preparation of intermediate M-361
Under the protection of argon, raw materials e-361 (58.64 g,300.00 mmol), raw materials b-330 (78.05 g,300.00 mmol) and K are added into a reaction bottle 2 CO 3 (62.19 g,450.00 mmol) and 1500mL toluene/ethanol/water (2:1:1) mixed solvent, pd (PPh) was added after three argon substitutions of air 3 ) 4 (3.47 g,3.00 mmol) and stirring the mixture, heating the above system to reflux for 4.5 hours, cooling to room temperature after the reaction, suction filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate M-361 (58.96 g, yield 79%), wherein the HPLC purity is more than or equal to 99.75%. Mass spectrum m/z:248.0355 (theory: 248.0365).
(2) Preparation of intermediate b-361
Under the protection of argon, intermediate M-361 (49.75 g,200.00 mmol), raw material g-361 (55.87 g,220.00 mmol), KOAc (29.44 g,300.00 mmol), DMF (500 mL) and Pd (dppf) Cl were added after replacing the air with argon three times 2 (1.46 g,2.00 mmol), stirring the mixture, heating the mixture for 5 hours, after the reaction, adding distilled water, extracting with dichloromethane for 3 times, separating the liquid, washing the organic phase with saturated saline water for three times, then drying with anhydrous magnesium sulfate, rotary evaporating to concentrate the solvent, cooling and crystallizing, suction filtering, and recrystallizing the obtained solid with toluene to obtain an intermediate b-361 (57.17 g, yield 84%), wherein the HPLC purity is not less than 99.67%. Mass spectrum m/z:340.1620 (theory: 340.1606).
Following the procedure described above for the preparation of intermediates b-361, in accordance with synthetic example 2, the present invention also synthesizes the following intermediates:
Synthesis example 3 preparation of Compound 1
Under the protection of argon, the reaction flask was charged with raw material a-1 (26.00 g,80.00 mmol), raw material b-1 (51.87 g,162.00 mmol) and K 3 PO 4 Aqueous solution (44.57 g,210.00 mmol) then 300mL toluene was added and after three air substitutions with argon Pd (OAc) was added 2 (0.22 g,1.00 mmol), DPPF (0.55 g,1.00 mmol), stirring, heating and refluxing for reaction for 8 hours, sampling the spot plate, and completing the reaction. Naturally cooling to room temperature, suction filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate A-1 (32.66 g, yield 74%). HPLC purity is more than or equal to 99.79%. Mass spectrum m/z:551.1870 (theory: 551.1885).
Under the protection of argon, the intermediate A-1 (28.96 g,52.50 mmol), the raw material d-1 (11.25 g,50.00 mmol), naOt-Bu (12.01 g,125.00 mmol), 200mL toluene and Pd were added after three replacements of air with argon 2 (dba) 3 (0.46 g,0.50 mmol), (1 mL,0.5 mmol) P (t-Bu) 3 (0.5M toluene solution), the mixture was stirred, heated under reflux for 12 hours, the spot plate was sampled and the reaction was complete. Naturally cooling to room temperature, filtering with diatomite, rotationally evaporating to concentrate solvent, cooling for crystallization, suction filtering, recrystallizing the obtained solid with ethyl acetate to obtain solid compound 1 (22.96 g, yield 66%), and detecting solid purity of not less than 99.88% by HPLC. Mass spectrum m/z:695.2061 (theory: 695.2072). Theoretical element content (%) C 47 H 28 F 3 NO 2 : c,81.14; h,4.06; n,2.01. Measured element content (%): c,81.17; h,4.02; n,2.04. Synthesis example 4]Preparation of Compound 15
According to the same manner as that of Compound 1 of Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-15 and d-15, respectively, to give Compound 15 (18.40 g), whose solid purity was not less than 99.93% as measured by HPLC. Mass spectrum m/z:525.1744 (theory: 525.1729). Theoretical element content (%) C 38 H 23 NO 2 : c,86.84; h,4.41; n,2.66. Measured element content (%): c,86.88; h,4.43; n,2.62.
Synthesis example 5 preparation of Compound 28
According to the same manner as that of Compound 1 in Synthesis example 3, a-1, b-1 and d-1 were replaced with equimolar amounts of a-28, b-28 and d-28, respectively, to give Compound 28 (19.64 g), whose solid purity was not less than 99.95% as measured by HPLC. Mass spectrum m/z:577.1776 (theory: 577.1790). Theoretical element content (%)C 40 H 23 N 3 O 2 : c,83.17; h,4.01; n,7.27. Measured element content (%): c,83.13; h,4.03; n,7.23.
Synthesis example 6 preparation of Compound 41
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-15 and d-41, respectively, to give Compound 41 (19.70 g), whose solid purity was not less than 99.91% as measured by HPLC. Mass spectrum m/z:615.1850 (theory: 615.1834). Theoretical element content (%) C 44 H 25 NO 3 : c,85.84; h,4.09; n,2.28. Measured element content (%): c,85.81; h,4.06; n,2.24.
Synthesis example 7 preparation of Compound 52
According to the same manner as that of Compound 1 of Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-52 and d-52, respectively, to give Compound 52 (19.15 g), whose solid purity was not less than 99.94% as measured by HPLC. Mass spectrum m/z:617.1726 (theory: 617.1739). Theoretical element content (%) C 42 H 23 N 3 O 3 : c,81.67; h,3.75; n,6.80. Measured element content (%): c,81.65; h,3.72; n,6.84.
Synthesis example 8 preparation of Compound 86
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-15 and d-86, respectively, to give Compound 86 (19.88 g), whose solid purity was not less than 99.96% as measured by HPLC. Mass spectrum m/z:611.2753 (theory: 611.2762). Management deviceTheoretical element content (%) C 44 H 29 D 4 NO 2 : c,86.39; h,6.10; n,2.29. Measured element content (%): c,86.34; h,6.13; n,2.25.
Synthesis example 9 preparation of Compound 96
According to the same manner as that of Compound 1 in Synthesis example 3, a-1, b-1 and d-1 were replaced with equimolar amounts of a-96, b-15 and d-96, respectively, to give Compound 96 (20.02 g), and the purity of the solid was not less than 99.93% as measured by HPLC. Mass spectrum m/z:597.2585 (theory: 597.2575). Theoretical element content (%) C 43 H 23 D 6 NO 2 : c,86.40; h,5.09; n,2.34. Measured element content (%): c,86.44; h,5.06; n,2.32.
Synthesis example 10 preparation of Compound 106
According to the same manner as that of Compound 1 of Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-15 and d-106, respectively, to give Compound 106 (20.41 g), whose solid purity was not less than 99.96% as measured by HPLC. Mass spectrum m/z:591.1845 (theory: 591.1834). Theoretical element content (%) C 42 H 25 NO 3 : c,85.26; h,4.26; n,2.37. Measured element content (%): 85.22; h,4.29; n,2.33.
Synthesis example 11 preparation of Compound 155
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-155 and d-155, respectively, to give Compound 155 (25.19 g), whose purity by HPLC was not less than 99.92%. Mass Spectrometry m/z:825.2276 (theory: 825.2291). Theoretical element content (%) C 56 H 31 F 4 NO 2 : c,81.44; h,3.78; n,1.70. Measured element content (%): c,81.47; h,3.73; n,1.74.
Synthesis example 12 preparation of Compound 162
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-162 and d-162, respectively, to give Compound 162 (24.54 g), and the purity of the solid was not less than 99.97% as measured by HPLC. Mass spectrum m/z:817.2633 (theory: 817.2617). Theoretical element content (%) C 60 H 35 NO 3 : c,88.11; h,4.31; n,1.71. Measured element content (%): 88.15; h,4.34; n,1.69.
Synthesis example 13 preparation of Compound 176
Under the protection of argon, the reaction flask was charged with raw material a-176 (33.67 g,120.00 mmol), raw material b-176 (32.29 g,120.00 mmol), and then K 3 PO 4 Aqueous solution (33.96 g,160 mmol), 400mL toluene, argon air three times after adding Pd (OAc) 2 (0.32 g,1.43 mmol) DPPF (0.79 g,1.43 mmol) was reacted under stirring and heating reflux for 7 hours, and the reaction was completed at the spot plate. Naturally cooling to room temperature, suction filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate A-176 (30.85 g, yield 75%). The HPLC purity is more than or equal to 99.73 percent. Mass spectrum m/z:342.0548 (theory: 342.0560).
To the reaction flask was added intermediate A-176 (27.42 g,80.00 mmol), starting material c-176 (19.53 g,80.00 mmol), under argon, followed by K 3 PO 4 Aqueous solution (23.35 g,110 mmol), 300mL toluene, argon air three times after adding Pd (OAc) 2 (0.21 g,0.95 mmol), DPPF (0.53 g,0.95 mmol), and the reaction was stirred and heated at reflux for 6 hours, the spot plate was sampled and the reaction was complete. Naturally cooling to room temperature, suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain intermediate B-176 (24.45 g, yield 72%). HPLC purity is more than or equal to 99.70%. Mass spectrum m/z:424.1223 (theory: 424.1212).
Under the protection of argon, adding an intermediate B-176 (22.28 g,52.50 mmol), a raw material d-176 (11.70 g,50.00 mmol), naOt-Bu (12.01 g,125.00 mmol) and 250mL toluene into a reaction bottle, stirring and mixing, replacing air with argon for three times, and adding Pd 2 (dba) 3 (0.46 g,0.50 mmol), (1 mL,0.5 mmol) P (t-Bu) 3 (0.5M toluene solution), stirring, heating and refluxing for reaction for 12 hours, sampling the spot plate, and completely reacting; naturally cooling to room temperature, filtering with diatomite, rotationally evaporating to concentrate solvent, cooling for crystallization, suction filtering, recrystallizing the obtained solid with ethyl acetate to obtain solid compound 176 (19.64 g, yield 68%), and detecting solid purity of not less than 99.90% by HPLC. Mass spectrum m/z:577.1779 (theory: 577.1790). Theoretical element content (%) C 40 H 23 N 3 O 2 : c,83.17; h,4.01; n,7.27. Measured element content (%): c,83.13; h,4.05; n,7.24.
Synthesis example 14 preparation of Compound 184
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-184 and d-184, respectively, to give Compound 184 (23.00 g), whose solid purity was not less than 99.91% as measured by HPLC. Mass spectrum m/z:741.2318 (theory: 741.2304). Theoretical element content (%) C 54 H 31 NO 3 : c,87.43; h,4.21; n,1.89. Measured element content (%): c,87.46; h,4.25; n,1.84.
Synthesis example 15 preparation of Compound 214
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-214 and d-214, respectively, to give Compound 214 (21.38 g), whose solid purity was not less than 99.88% as measured by HPLC. Mass spectrum m/z:700.2720 (theory: 700.2712). Theoretical element content (%) C 50 H 20 D 9 NO 3 : c,85.69; h,5.46; n,2.00. Measured element content (%): c,85.67; h,5.42; n,2.03.
Synthesis example 16 preparation of Compound 225
According to the same manner as that of Compound 1 in Synthesis example 3, a-1, b-1 and d-1 were replaced with equimolar amounts of a-225, b-225 and d-225, respectively, to give Compound 225 (22.30 g), and the purity of the solid was not less than 99.94% as measured by HPLC. Mass spectrum m/z:707.1910 (theory: 707.1919). Theoretical element content (%) C 50 H 29 NO 2 S: c,84.84; h,4.13; n,1.98. Measured element content (%): c,84.88; h,4.15; n,1.95.
Synthesis example 17 preparation of Compound 266
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with b-266 and d-266 in equimolar amounts, respectively, to give Compound 266 (21.54 g), which was found to have a solid purity of 99.90% or more by HPLC. Mass spectrum m/z:662.1586 (theory: 662.1565). Theoretical element content (%) C 43 H 26 N 4 S 2 : c,77.92; h,3.95; n,8.45. Measured element content (%): c,77.97; h,3.98; n,8.41.
Synthesis example 18 preparation of Compound 277
According to the same manner as that of Compound 1 of Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-277 and d-277, respectively, to give Compound 277 (22.14 g), which was found to have a solid purity of 99.92% or more by HPLC. Mass spectrum m/z:691.1451 (theory: 691.1462). Theoretical element content (%) C 46 H 29 NS 3 : c,79.85; h,4.22; n,2.02. Measured element content (%): c,79.82; h,4.27; n,2.00.
Synthesis example 19 preparation of Compound 285
According to the same manner as that for compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-15, b-266 and d-285, respectively, to give compound 285 (20.85 g), and the purity of the solid was not less than 99.97% as measured by HPLC. Mass spectrum m/z:631.1621 (theory: 631.1606). Theoretical element content (%) C 44 H 25 NO 2 S: c,83.65; h,3.99; n,2.22. Measured element content (%): c,83.68; h,3.95; n,2.20.
Synthesis example 20 preparation of Compound 303
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-303 and d-303, respectively, to give Compound 303 (22.62 g), whose solid purity was not less than 99.94% as measured by HPLC. Mass spectrum m/z:717.2481 (theory: 717.2493). Theoretical element content (%) C 50 H 35 D 2 NS 2 : c,83.64; h,5.47; n,1.95. Measured element content (%): c,83.61; h,5.43; n,1.98.
Synthesis example 21 preparation of Compound 308
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-266 and d-308, respectively, to give Compound 308 (20.83 g), whose solid purity was not less than 99.95% as measured by HPLC. Mass spectrum m/z:640.2015 (theory: 640.2024). Theoretical element content (%) C 44 H 20 D 7 NS 2 : c,82.46; h,5.35; n,2.19. Measured element content (%): c,82.42; h,5.32; n,2.16.
Synthesis example 22 preparation of Compound 322
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-322 and d-322, respectively, to give Compound 322 (26.31 g), whose solid purity was not less than 99.98% as measured by HPLC. Mass spectrum m/z:876.2620 (theory: 876.2633). Theoretical element content (%) C 62 H 40 N 2 S 2 : c,84.90; h,4.60; n,3.19. Measured element content (%): c,84.88; h,4.63; n,3.16.
Synthesis example 23 preparation of Compound 330
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-330 and d-330, respectively, to give Compound 330 (23.99 g), whose solid purity was not less than 99.96% as measured by HPLC. Mass spectrum m/z:773.2226 (theory: 773.2211). Theoretical element content (%) C 55 H 35 NS 2 : c,85.35; h,4.56; n,1.81. Measured element content (%): c,85.31; h,4.52; n,1.84.
Synthesis example 24 preparation of Compound 361
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-361 and d-361, respectively, to give Compound 361 (25.75 g), whose solid purity was not less than 99.93% as measured by HPLC. Mass spectrum m/z:843.2883 (theory: 843.2870). Theoretical element content (%) C 60 H 29 D 8 NS 2 : c,85.37; h,5.37; n,1.66. Measured element content (%): c,85.34; h,5.35; n,1.69.
Synthesis example 25 preparation of Compound 384
According to the same manner as that of Compound 1 in Synthesis example 3, a-1, b-1 and d-1 were replaced with equimolar amounts of a-384, b-266 and d-384, respectively, to give Compound 384 (21.57 g), whose solid purity was not less than 99.87% as measured by HPLC. Mass spectrum m/z:684.1682 (theory: 684.1694). Theoretical element content (%) C 47 H 28 N 2 S 2 : c,82.43; h,4.12; n,4.09. Measured element content (%): c,82.40; h,4.16; n,4.06.
Synthesis example 26 preparation of Compound 391
According to the same manner as that of Compound 1 in Synthesis example 3, a-1, b-1 and d-1 were replaced with equimolar amounts of a-391, b-266 and d-391, respectively, to give Compound 391 (20.83 g), which was found to have a solid purity of 99.92% or more by HPLC. Mass spectrum m/z:640.1119 (theory: 640.1102). Theoretical element content (%) C 41 H 24 N 2 S 3 : c,76.84; h,3.78; n,4.37. Actual measurement elementContent (%): c,76.87; h,3.75; n,4.35.
Synthesis example 27 preparation of Compound 409
According to the same manner as that of Compound 1 in Synthesis example 3, a-1, b-1 and d-1 were replaced with equimolar amounts of a-409, b-409 and d-409, respectively, to give Compound 409 (19.99 g), and the purity of the solid as measured by HPLC was not less than 99.96%. Mass spectrum m/z:644.2261 (theory: 644.2275). Theoretical element content (%) C 44 H 16 D 11 NS 2 : c,81.95; h,5.94; n,2.17. Measured element content (%): c,81.91; h,5.92; n,2.14.
Synthesis example 28 preparation of Compound 425
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-425 and d-425, respectively, to give Compound 425 (24.03 g), whose purity by HPLC was not less than 99.91%. Mass spectrum m/z:787.2107 (theory: 787.2116). Theoretical element content (%) C 54 H 33 N 3 S 2 : c,83.21; h,4.22; n,5.33. Measured element content (%): c,83.23; h,4.26; n,5.30.
Synthesis example 29 preparation of Compound 434
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-434 and d-434, respectively, to give Compound 434 (27.37 g), whose solid purity was not less than 99.86% as measured by HPLC. Mass spectrum m/z:911.2668 (theory: 911.2680). Theoretical element content (%) C 66 H 41 NS 2 : c,86.90; h,4.53; n,1.54. Measured element content (%): c,86.92; h,4.56; n,1.58.
Synthesis example 30 preparation of Compound 478
According to the same manner as that for preparing compound 176 of synthetic example 13, b-176, c-176 and d-176 are replaced with equimolar amounts of b-300, c-478 and d-478, respectively, to obtain compound 478 (16.47 g), and the purity of the solid is not less than 99.95% as measured by HPLC. Mass spectrum m/z:491.1358 (theory: 491.1344). Theoretical element content (%) C 34 H 21 And (2) NOS: c,83.07; h,4.31; n,2.85. Measured element content (%): c,83.11; h,4.34; n,2.82.
Synthesis example 31 preparation of Compound 498
According to the same manner as that for compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-28, c-498 and d-106, respectively, to give compound 498 (19.56 g), and the purity of the solid was not less than 99.92% as measured by HPLC. Mass spectrum m/z:601.2051 (theory: 601.2042). Theoretical element content (%) C 44 H 27 NO 2 : c,87.83; h,4.52; n,2.33. Measured element content (%): c,87.80; h,4.56; n,2.31.
Synthesis example 32 preparation of Compound 513
To a reaction flask was added intermediate a-513 (19.69 g,80.00 mmol), starting material b-15 (19.53 g,80.00 mmol), under argon, followed by K 3 PO 4 Aqueous solution (23.35 g,110 mmol), 300mL toluene, argon air three times after adding Pd (OAc) 2 (0.21 g,0.95 mmol), DPPF (0.08 g,0.14 mmol), stirring, heating and refluxing for reaction for 6 hours, sampling the spot plate, and completing the reaction. Naturally cooling to room temperature, suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain an intermediate A-513 (17.00 g, yield 75%). The HPLC purity is more than or equal to 99.73 percent. Mass spectrum m/z:283.0981 (theory: 283.0997).
Under the protection of argon, the reaction flask was charged with intermediate A-513 (14.87 g,52.50 mmol), starting material d-513 (16.21 g,50.00 mmol), naOt-Bu (12.01 g,125.00 mmol), 250mL toluene, and Pd after three replacements of air with argon 2 (dba) 3 (0.23 g,0.25 mmol), (1 mL,0.5 mmol) P (t-Bu) 3 (0.5M toluene solution), stirring and heating reflux reaction were carried out for 12 hours, the spot plate was sampled, and the reaction was completed. Naturally cooling to room temperature, filtering with diatomite, removing solvent by rotary evaporation, cooling for crystallization, suction filtering, recrystallizing the obtained solid with ethyl acetate, and finally obtaining a solid compound 513 (16.59 g, yield 63%), wherein the purity of the solid detected by HPLC is more than or equal to 99.96%. Mass spectrum m/z:526.1693 (theory: 526.1681). Theoretical element content (%) C 37 H 22 N 2 O 2 : c,84.39; h,4.21; n,5.32. Measured element content (%): c,84.35; h,4.24; n,5.30.
Synthesis example 33 preparation of Compound 531
According to the same manner as that for compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-531, c-531 and d-531, respectively, to give compound 531 (20.52 g), and the purity of the solid was not less than 99.85% as measured by HPLC. Mass spectrum m/z:661.2842 (theory: 661.2826). Theoretical element content (%) C 48 H 19 D 10 NO 2 : c,87.11; h,5.94; n,2.12. Measured element content (%): c,87.15; h,5.96; n,2.09.
Synthesis example 34 preparation of Compound 578
According to the same manner as that for compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-266, c-578 and d-578, respectively, to give compound 578 (21.18 g), and the purity of the solid was not less than 99.97% as measured by HPLC. Mass spectrum m/z:641.1822 (theory: 641.1813). Theoretical element content (%) C 46 H 27 And (2) NOS: c,86.09; h,4.24; n,2.18. Measured element content (%): c,86.14; h,4.27; n,2.14.
Synthesis example 35 preparation of Compound 588
According to the same manner as that of Compound 513 in Synthesis example 32, b-28 and d-513 were replaced with equimolar amounts of b-588 and d-588, respectively, to give Compound 588 (23.44 g), whose purity by HPLC was not less than 99.92%. Mass spectrum m/z:755.2636 (theory: 755.2647). Theoretical element content (%) C 56 H 37 NS: c,88.97; h,4.93; n,1.85. Measured element content (%): c,88.93; h,4.91; n,1.81.
Synthesis example 36 preparation of Compound 599
According to the same manner as that described in Compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-330, c-599 and d-599, respectively, to give Compound 599 (21.90 g), and the purity of the solid was not less than 99.94% as measured by HPLC. Mass spectrum m/z:717.2139 (theory: 717.2126). Theoretical element content (%) C 52 H 31 And (2) NOS: c,87.00; h,4.35; n,1.95. Measured element content (%): c,87.02; h,4.38; n,1.99.
Synthesis example 37 preparation of Compound 611
According to the same manner as that for compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-330, c-611 and d-611, respectively, to give compound 611 (23.85 g), and the purity of the solid was not less than 99.90% as measured by HPLC. Mass spectrum m/z:756.3210 (theory: 756.3223). Theoretical element content (%) C 54 H 36 D 5 And (2) NOS: c,85.68; h,6.12; n,1.85. Measured element content (%): c,85.64; h,6.15; n,1.81.
Synthesis example 38 preparation of Compound 622
According to the same manner as that of compound 513 of Synthesis example 32, a-513, b-28 and d-513 were replaced with equimolar amounts of a-622, b-425 and d-622, respectively, to give compound 622 (22.59 g), whose solid purity was not less than 99.91% as measured by HPLC. Mass spectrum m/z:742.2433 (theory: 742.2443). Theoretical element content (%) C 54 H 34 N 2 S: c,87.30; h,4.61; n,3.77. Measured element content (%): c,87.33; h,4.65; n,3.74.
Synthesis example 39 preparation of Compound 627
According to the same manner as that of compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-627, c-627 and d-627, respectively, to give compound 627 (22.91 g), and the purity of the solid was not less than 99.94% as measured by HPLC. Mass spectrum m/z:738.2154 (theory: 738.2163). Theoretical element content (%) C 51 H 34 N 2 S 2 : c,82.89; h,4.64; n,3.79. Measured element content (%): c,82.85; h,4.67; n,3.77.
Synthesis example 40 preparation of Compound 647
According to the same manner as that described in Compound 176 of Synthesis example 13, b-176, c-176 and d-176 were replaced with equimolar amounts of b-647, c-578 and d-277, respectively, to give Compound 647 (23.52 g), whose solid purity was not less than 99.95% as measured by HPLC. Mass spectrum m/z:783.2068 (theory: 783.2054). Theoretical element content (%) C 56 H 33 NS 2 : c,85.79; h,4.24; n,1.79. Measured element content (%): c,85.76; h,4.28; n,1.76.
Synthesis example 41 preparation of Compound 674
According to the same manner as that of Compound 1 in Synthesis example 3, b-1 and d-1 were replaced with equimolar amounts of b-674 and d-674, respectively, to give Compound 674 (24.19 g), and the purity of the solid was not less than 99.93% as measured by HPLC. Mass spectrum m/z:767.3564 (theory: 767.3552). Theoretical element content (%) C 59 H 45 N: c,92.27; h,5.91; n,1.82. Measured element content (%): c,92.30; h,5.94; n,1.77.
Synthesis example 42 preparation of Compound 746
According to the same manner as that of compound 513 of Synthesis example 32, b-28 and d-513 were replaced with equimolar amounts of b-746 and d-746, respectively, to give compound 746 (20.95 g), whose solid purity was not less than 99.97% as measured by HPLC. Mass spectrum m/z:686.2713 (theory: 686.2722). Theoretical element content (%) C 52 H 34 N 2 : c,90.93; h,4.99; n,4.08. Measured element content (%): c,90.96; h,4.95；N，4.06。
Device example 1-1: measurement of refractive index and glass transition temperature
The refractive index (n) was measured by using an M-2000 spectroscopic ellipsometer from J.A.Woollam, U.S.A., the glass substrate was first subjected to UV ozone cleaning for 20 minutes, and then transferred to a vacuum vapor deposition apparatus, and the vacuum degree in the system was controlled at 1X 10 -3 Pa, compound 1, compound 15, compound 28, compound 41, compound 52, compound 86, compound 96, compound 106, compound 155, compound 162, compound 176, compound 184, compound 214, compound 225, compound 266, compound 277, compound 285, compound 303, compound 308, compound 322, compound 330, compound 361, compound 384, compound 391, compound 409, compound 425, compound 434, compound 478, compound 498, compound 513, compound 531, compound 578, compound 588, compound 599, compound 611, compound 622, compound 627, compound 647, compound 674, compound 746, comparative compound 1, comparative compound 2, comparative compound 3, and comparative compound 4 were deposited on a glass substrate to form a film sample having a deposition thickness of 80nm and a deposition rate of 0.1nm/s.
The film samples prepared above were tested for refractive index n at 450nm, 525nm, 620nm, respectively, and the refractive index test results are shown in table 1.
The glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC, german relaxation company DSC204F1 differential scanning calorimeter), test samples: the present invention was conducted for compound 1, compound 15, compound 28, compound 41, compound 52, compound 86, compound 96, compound 106, compound 155, compound 162, compound 176, compound 184, compound 214, compound 225, compound 266, compound 277, compound 285, compound 303, compound 308, compound 322, compound 330, compound 361, compound 384, compound 391, compound 409, compound 425, compound 434, compound 478, compound 498, compound 513, compound 531, compound 578, compound 588, compound 599, compound 611, compound 622, compound 627, compound 647, compound 674, compound 746, and comparative compound 1, comparative compound 2, comparative compound 3, comparative compound 4, individually tested for each sample at a mass of 5mg. The test atmosphere is nitrogen, and the flow rate of the nitrogen is 50mL/min; the temperature rising rate is 10 ℃/min, and the temperature range is 50-350 ℃. The glass transition temperature (Tg) test results are shown in table 1:
Table 1:
according to the results in Table 1, the compound of the invention has higher refractive index for visible light with the wavelength of 450 nm-620 nm, meets the requirement of an organic electroluminescent device on refractive index, has higher glass transition temperature and has good film stability.
Device examples 2 to 1
Firstly, a glass substrate on which ITO (15 nm)/Ag (150 nm)/ITO (15 nm) is evaporated is put in distilled water for cleaning for 2 times, ultrasonic washing is performed for 30 minutes, then distilled water is used for repeatedly cleaning for 2 times, ultrasonic washing is performed for 10 minutes, after the distilled water cleaning is finished, ultrasonic washing is performed sequentially by using isopropanol, acetone and methanol solvents, drying is performed on a hot plate heated to 120 ℃, the dried substrate is transferred to a plasma cleaning machine, and after 5 minutes of washing, the substrate is transferred to an evaporation machine.
Then, HT-1 and P-1 (HT-1:P-1=97:3 mass ratio) are evaporated on the cleaned ITO (15 nm)/Ag (150 nm)/ITO (15 nm) substrate to serve as a hole injection layer, the evaporation thickness is 10nm, HT-1 is evaporated on the hole injection layer to serve as a hole transport layer, the evaporation thickness is 130nm, BH-1 is evaporated on the hole transport layer in a vacuum manner to serve as a main material, BD-1 is evaporated as a doping material (BH-1:BD-1=97:3 mass ratio) to jointly form a light-emitting layer, the evaporation thickness is 20nm, ET-1 and Liq (ET-1:Liq=1:1 mass ratio) are evaporated on the light-emitting layer to serve as an electron transport layer, the evaporation thickness is 35nm, liF is evaporated on the electron transport layer to serve as an electron injection layer, the evaporation thickness is 1nm, and Mg is evaporated on the electron injection layer: ag (Mg: ag=1:9 mass ratio) is used as a cathode, the evaporation thickness is 15nm, then the compound 1 of the invention is used as a covering layer by vacuum evaporation on the cathode, and the evaporation thickness is 70nm, so that the organic electroluminescent device is prepared.
Device examples 2-2 to 2-40
An organic electroluminescent device was produced by the same production method as in device example 1, except that compound 15, compound 28, compound 41, compound 52, compound 86, compound 96, compound 106, compound 155, compound 162, compound 176, compound 184, compound 214, compound 225, compound 266, compound 277, compound 285, compound 303, compound 308, compound 322, compound 330, compound 361, compound 384, compound 391, compound 409, compound 425, compound 434, compound 478, compound 498, compound 513, compound 531, compound 578, compound 588, compound 599, compound 611, compound 622, compound 627, compound 647, compound 674 and compound 746 were used as the capping layers instead of the compound 1 in device example 1, respectively.
Comparative device examples 1 to 4
An organic electroluminescent device was manufactured by the same manufacturing method as device example 1, except that compound 1 in device example 1 was replaced with comparative compound 1, comparative compound 2, comparative compound 3, and comparative compound 4, respectively, as a cover layer.
Test software, a computer, a K2400 digital source list manufactured by Keithley company, U.S. and a PR788 spectral scanning luminance meter manufactured by Photo Research, U.S. are combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature. The results of testing the light emitting characteristics of the devices 1 to 40 in the device examples according to the present invention, and the organic electroluminescent devices obtained in the comparative device examples 1 to 4 are shown in table 2 below.
Table 2:
as shown in the results of Table 2, when the carbazole derivative is applied to the cover layer of the organic electroluminescent device, the carbazole derivative has higher refractive index, so that the light extraction efficiency inside the organic electroluminescent device can be effectively improved, and the luminous efficiency is further improved, meanwhile, the carbazole derivative has higher glass transition temperature and higher thermal stability, and the thin film after vapor deposition film formation has good stability and is not easy to crystallize, and meanwhile, oxygen and water in the air can be isolated, the internal damage of the device is avoided, and the service life of the organic electroluminescent device is prolonged.
It should be noted that while the present invention has been specifically described with reference to individual embodiments, it will be apparent to those skilled in the art that numerous modifications and variations can be made without departing from the principles of the present invention, and such modifications and variations fall within the scope of the present invention.
Claims (10)
1. Use of a carbazole derivative in a cover layer of an organic electroluminescent device, characterized in that the carbazole derivative is represented by the following formula I:
ar is selected from any one of the following structures in formula 2 or formula 3:
the X is 1 Independently selected from C (R) 2 ) Or N, said X is independently selected from C (R 3 ) Or N, said X 2 Selected from O, S, C (R) 4 R 5 ) Or N (R) 6 )；
And L is equal to 3 X bonded to Ar is selected from C; and L is equal to 3 Bonded X 1 Selected from C and L 2 Bonded X 1 Selected from C;
the R is 1 、R 2 、R 3 Independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said n 1 Selected from 0, 1 or 2;
having two or more R' s 2 When present, two or more R' s 2 Identical or different from each other, or adjacent two R' s 2 Can be linked to form a substituted or unsubstituted ring, with two or more R' s 3 When present, two or more R' s 3 Identical or different from each other, or adjacent two R' s 3 Can be connected to form any one of a substituted or unsubstituted benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring or a C3-C7 aliphatic ring;
the R is 4 、R 5 、R 6 Independently selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or R is 4 、R 5 Can be connected to be substituted or notSubstituted rings;
the L is 1 Independently selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, and substituted or unsubstituted C2-C30 heteroarylene;
the L is 2 、L 3 Independently selected from any one or more of single bond, substituted or unsubstituted following groups: phenylene, biphenylene, terphenyl, naphthylene, anthrylene, phenanthrylene, triphenylene, benzocyclopropylene, benzocyclobutene, benzocyclopentylene, benzocyclohexylene, pyridylene, pyrimidinylene, pyrazinylene, pyridazinylene, triazinylene, quinolinylene, isoquinolylene, quinazolinylene, quinoxalinylene, phenanthroline, naphthyridine, benzothiophenylene, benzofuranylene, dibenzothiophenylene, dibenzofuranylene, fluorenylene, carbazolylene, N-heterobenzothiophenylene, N-heterobenzofuranylene, N-heterodibenzothiophenylene, N-heterodibenzofuranylene;
The Ar is as follows 1 Independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, unsubstituted or C6-C30 aryl substituted with one or more Ra, or selected from any one of structures represented by the following formulas 4-1 to 4-8:
in the formulas 4-1 to 4-8,
z is independently selected from C (Rb) or N, and at least one Z in each group of formulas 4-1 to 4-5 is selected from N;
the Y is selected from C (Rb) or N;
the M is 1 Selected from O, S, C (RcRd) or N (Re), said M 2 Selected from C (Rc) or N, said M 3 Selected from O, S, C (RcRd) or N (Re);
the Ra is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl and substituted or unsubstituted C6-C30 aryl; when two or more Ra are present, two or more Ra may be the same or different from each other, or two Ra adjacent to each other may be linked to form a substituted or unsubstituted ring;
the Rb is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; when two or more Rb are present, two or more Rb are the same or different from each other or adjacent two Rb may be linked to form a substituted or unsubstituted ring;
The Rf is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said m is selected from 0, 1 or 2;
the Rc, rd and Re are independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atoms, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or Rc, rd form a substituted or unsubstituted ring;
the Ar is as follows 2 Independently selected from hydrogen, deuterium, tritium, cyano, halogen atoms, nitro, hydroxy, trifluoromethyl, substituted or unsubstituted C1-C12 alkanesA group, a substituted or unsubstituted C2-C12 alkenyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C2-C30 heteroaryl group.
2. Use of a carbazole derivative as claimed in claim 1 in a cover layer of an organic electroluminescent device, characterized in that Ar 1 Selected from any one of substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, or selected from structures represented by formulas 4-1 to 4-8, or selected from any one of the following groups:
said E is selected from C3-C7 aliphatic rings which are unsubstituted or substituted by one or more Ra,
the Ra is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen atom, nitro, hydroxyl, trifluoromethyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl;
the m is 1 Independently selected from 0, 1, 2, 3, 4 or 5, said m 2 Independently selected from 0, 1, 2, 3 or 4, said m 3 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, said m 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said m5 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11;
When two or more Ra exist, the two or more Ra are the same or different from each other, or a substituted or unsubstituted ring is attached between two Ra adjacent.
3. A carbazole derivative according to claim 1Use of Ar in the coating of organic electroluminescent devices, characterized in that 1 Any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane which are unsubstituted or substituted by any one or more substituents "deuterium, tritium, cyano, halogen atom, C1-C6 alkyl", or any one of the following groups:
the Ra is independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, hydroxy, halogen atom, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutyl, cyclopentylalkyl, cycloheptane, adamantyl, norbornane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthryl, phenanthryl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, deuteromethyl, deuteroethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornane methyl substituted adamantyl, ethyl substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylyl, deuterated fluorenyl, fluoro substituted phenyl, fluoro substituted biphenyl, cyano substituted phenyl, cyano substituted biphenyl, methyl substituted phenyl, methyl substituted biphenyl, ethyl substituted phenyl, ethyl substituted biphenyl, isopropyl substituted phenyl, isopropyl substituted biphenyl, tert-butyl substituted phenyl, tert-butyl substituted biphenyl, trifluoromethyl substituted phenyl, adamantyl substituted biphenyl, norbornyl substituted phenyl, norbornyl substituted biphenyl, methyl substituted naphthyl, ethyl substituted naphthyl, isopropyl substituted naphthyl, any one of tert-butyl substituted naphthyl, deuterated methyl substituted phenyl, deuterated isopropyl substituted phenyl and deuterated tert-butyl substituted phenyl;
The Rb is independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthracenyl, phenanthryl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiophenyl, and the like deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylene, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thiophenyl, deuterated benzothienyl, deuterated dibenzothiophenyl, deuterated carbazolyl, deuterated pyridinyl, deuterated pyrimidinyl, fluoro-substituted phenyl, fluoro-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, any one of ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, trifluoromethyl-substituted biphenyl, adamantyl-substituted phenyl, adamantyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl;
The Rf is independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, halogen, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexen, benzocycloheptane, naphthyl, anthracenyl, phenanthryl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, benzothiophenyl, and the like deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated sec-butyl, deuterated tert-butyl, deuterated adamantyl, deuterated norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylene, deuterated fluorenyl, deuterated furanyl, deuterated benzofuranyl, deuterated dibenzofuranyl, deuterated thiophenyl, deuterated benzothienyl, deuterated dibenzothiophenyl, deuterated carbazolyl, deuterated pyridinyl, deuterated pyrimidinyl, fluoro-substituted phenyl, fluoro-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, any one of ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, trifluoromethyl-substituted biphenyl, adamantyl-substituted phenyl, adamantyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl;
The m is 1 Independently selected from 0, 1, 2, 3, 4 or 5, said m 2 Independently selected from 0, 1, 2, 3 or 4, said m 3 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, said m 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said m 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said m 6 Independently selected from 0, 1, 2, 34, 5, 6, 7, 8, 9, 10, 11, 12 or 13, said m 7 Independently selected from 0, 1, 2 or 3, said m 8 Selected from 0, 1 or 2, said m 9 Independently selected from 0, 1, 2, 3, 4, 5 or 6, said m 10 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.
4. Use of a carbazole derivative as claimed in claim 1 in a cover layer of an organic electroluminescent device, characterized in that Ar 2 Any one selected from hydrogen, deuterium, cyano, nitro, hydroxyl, halogen atom, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantane, norbornane, or any one selected from the following groups:
the R is 7 Independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R 7 Can be linked to form a substituted or unsubstituted ring;
the X is 3 Independently selected from O, S, C (R 8 R 9 ) Or N (R) 10 ) The X is 4 Independently selected from C (R) 8 ) Or N;
the R is 8 、R 9 、R 10 Independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or R is 8 、R 9 Can be linked to form a substituted or unsubstituted ring;
the a 1 Independently selected from 0, 1, 2, 3, 4 or 5, said a 2 Independently selected from 0, 1, 2, 3 or 4, said a 3 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, said a 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, said a 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, said a 6 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, said a 7 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said a 8 Independently selected from 0, 1, 2 or 3, said a 9 Independently selected from 0, 1 or 2, said a 10 Independently selected from 0, 1, 2, 3, 4, 5 or 6.
5. Use of a carbazole derivative as claimed in claim 1 in a cover layer of an organic electroluminescent device, characterized in that the carbazole derivative is used as a material for the cover layer
Selected from any one of the following groups: />
The X is 2 Selected from O, S, C (R) 4 R 5 ) Or N (R) 6 )；
The R is 4 、R 5 、R 6 Independently selected from the group consisting of hydrogen, deuterium, tritium, cyano, nitro, hydroxy, trifluoromethyl, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, norbornane, goldAn adamantyl group, a deuteromethyl group, a deuteroethyl group, a deutero-n-propyl group, a deuteroisopropyl group, a deuterated tert-butyl group, a deuterated adamantyl group, a deuterated norbornyl group, a methyl-substituted adamantyl group, an ethyl-substituted adamantyl group, or the following groups which are unsubstituted or substituted with one or more groups selected from the group consisting of deuterium, cyano groups, trifluoromethyl groups, halogen atoms, C1 to C6 alkyl groups, adamantyl groups, and norbornyl groups: any one of phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexen, benzocycloheptane, naphthyl, anthryl, phenanthryl, triphenylene, fluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, carbazolyl; or R is 4 、R 5 Can be connected to form a spiro ring;
said n 3 Independently selected from 0, 1, 2, 3 or 4, said n 4 Independently selected from 0, 1, 2, 3, 4, 5 or 6, said n 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said n 6 Independently selected from 0, 1, 2 or 3, said n 7 Independently selected from 0, 1 or 2, said n 8 Independently selected from 0, 1, 2, 3, 4 or 5, said n 9 Independently selected from 0, 1, 2, 3, 4, 5, 6 or 7.
6. Use of a carbazole derivative as claimed in claim 1 in a cover layer of an organic electroluminescent device, characterized in that R is 1 、R 2 Independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen atoms, hydroxy, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexenyl, cycloheptane, norbornane, adamantane, phenyl, biphenyl, terphenyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexenyl, benzocycloheptane, naphthyl, anthracenyl, phenanthrenyl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9' -spirobifluorenyl, furanyl, benzofuranyl, and dibenzofuranyl Benzofuranyl, thienyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, deuteromethyl, deuteroethyl, deutero-n-propyl, deutero-isopropyl, deutero-n-butyl, deutero-isobutyl, deutero-sec-butyl, deutero-tert-butyl, deutero-adamantyl, deutero-norbornyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, deutero-phenyl, deutero-biphenyl, deutero-terphenyl, deutero-naphthyl, deutero-anthryl, deutero-phenanthryl, deutero-triphenylenyl, deutero-fluorenyl, deutero-furanyl, deutero-benzofuranyl, deutero-dibenzothienyl, deutero-carbazolyl fluorine-substituted phenyl, fluorine-substituted biphenyl, cyano-substituted phenyl, cyano-substituted biphenyl, methyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted phenyl, ethyl-substituted biphenyl, isopropyl-substituted phenyl, isopropyl-substituted biphenyl, tert-butyl-substituted phenyl, tert-butyl-substituted biphenyl, trifluoromethyl-substituted phenyl, adamantyl-substituted biphenyl, norbornyl-substituted phenyl, norbornyl-substituted biphenyl, methyl-substituted naphthyl, ethyl-substituted naphthyl, isopropyl-substituted naphthyl, tert-butyl-substituted naphthyl, deuterated methyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl.
7. Use of a carbazole derivative as claimed in claim 1 in a cover layer of an organic electroluminescent device, characterized in that the L 1 ～L 3 Independently selected from a single bond or any one of the following groups:
the Rx is independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, hydroxyl, halogen atom, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, deuteromethyl, deuteroethyl, deuterisopropyl, deuterated tert-butyl, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, deuterated pyridinyl, deuterated pyrimidinyl, deuterated pyridazinyl, deuterated pyrazinyl, deuterated quinolinyl, deuterated isoquinolinyl, or two adjacent Rx can be connected to form a substituted or unsubstituted benzene ring or naphthalene ring;
said b 1 Independently selected from 0, 1, 2, 3 or 4, said b 2 Independently selected from 0, 1, 2 or 3, said b 3 Independently selected from 0, 1 or 2, said b 4 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said b 5 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
8. Use of a carbazole derivative as claimed in claim 1 in a cover layer, wherein L is 1 ～L 3 Independently selected from a single bond or any one of the following groups:
9. use of a carbazole derivative as claimed in claim 1 in a cover layer, wherein the carbazole derivative is selected from any one of the following structures:
10. an organic electroluminescent device comprising an anode, an organic layer, a cathode, and a cover layer located outside at least one of the anode or the cathode, the cover layer comprising at least one or more of the carbazole derivatives as described in any one of claims 1 to 9.
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| CN202310063764.4A CN116209291A (en) | 2023-01-13 | 2023-01-13 | Application of carbazole derivative in organic electroluminescent device cover layer |
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| CN202310063764.4A CN116209291A (en) | 2023-01-13 | 2023-01-13 | Application of carbazole derivative in organic electroluminescent device cover layer |
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