CN114940650A - Aromatic amine compound containing phenylfluorene and organic electroluminescent device thereof - Google Patents

Aromatic amine compound containing phenylfluorene and organic electroluminescent device thereof Download PDF

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CN114940650A
CN114940650A CN202210728806.7A CN202210728806A CN114940650A CN 114940650 A CN114940650 A CN 114940650A CN 202210728806 A CN202210728806 A CN 202210728806A CN 114940650 A CN114940650 A CN 114940650A
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杜明珠
周雯庭
陆影
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Changchun Hyperions Technology Co Ltd
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Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to an aromatic amine compound containing phenylfluorene and an organic electroluminescent device thereof. The aromatic amine compound containing the phenylfluorene provided by the invention has good hole mobility, proper HOMO energy level and T1 value, and can improve the luminous efficiency of a device and reduce the driving voltage of the device. Compared with the prior art, the aromatic amine compound containing the phenylfluorene provided by the invention has a low deuterium atom ratio, and can reduce the production cost.

Description

Aromatic amine compound containing phenylfluorene and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an aromatic amine compound containing phenylfluorene and an organic electroluminescent device thereof.
Background
An Organic Light-Emitting Diode (hereinafter abbreviated as OLED) has the advantages of being Light and thin in body state, wide in viewing angle, fast in response, wide in use temperature range, low in energy consumption, high in efficiency, good in color purity, high in definition, flexible and the like, and has a good application prospect in the fields of illumination and display.
The classical OLED device is in a sandwich structure, a light emitting layer containing a luminescent material is arranged between a cathode and an anode, a certain working voltage is applied between the two electrodes, under the action of an electric field, holes and electrons are injected from the anode and the cathode respectively and reach the light emitting layer, excitons are generated by recombination and release energy, the excitons migrate again and transfer the energy to the luminescent material, the electrons in the molecules of the luminescent material are transited from a ground state to an excited state, and the electrons transit back to a stable ground state due to unstable excited state, so that the energy is released in the form of light and a luminescent phenomenon is generated. In order to improve the performance of OLED devices such as driving voltage, luminous efficiency, color purity and the like, more other organic functional layers are additionally arranged between the anode and the luminous layer and between the cathode and the luminous layer. In general, an organic functional layer between the anode and the light-emitting layer plays a role of injecting and transporting holes, and is called a hole transport region; the organic functional layer between the cathode and the light emitting layer functions to inject and transport electrons and is called an electron transport region. The hole transport region includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emission auxiliary layer, and the like, and the electron transport region includes one or more of an electron injection layer, an electron transport layer, a hole blocking layer, and the like.
Among them, the hole transport material should generally have high hole mobility, good thermal stability and film forming property, and particularly, the hole transport material as the light-emitting auxiliary layer should also have appropriate Highest Occupied Molecular Orbital (HOMO), triplet state energy level (T1), and the like, in order to achieve high energy level matching between layers including the light-emitting layer. The aromatic amine compound is one of the most widely used hole transport materials in the field of OLED at present, and the compound has the performances required by the hole transport materials, and the aromatic amine compounds with different structures are different in performances, can be used as different hole transport functional layers, and some can also be used as materials of light-emitting auxiliary layers. However, the types of aromatic amine compounds currently used in industry are limited, and development thereof is urgently required.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides an aromatic amine compound containing a phenylfluorene, which has a good hole transport ability, a suitable HOMO level and T1 value, a high glass transition temperature (Tg), and can effectively improve the properties of an OLED device, such as light-emitting efficiency, driving voltage, and service life, and has a structure represented by formula (I):
Figure BDA0003714051230000021
wherein, a is 1 、c 1 Each occurrence, identically or differently, is selected from 0,1, 2 or 3; b is 1 、d 1 Each occurrence, identically or differently, is selected from 0,1, 2,3 or 4; said e 1 、f 1 、g 1 、h 1 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4 or 5;
a is described 1 、b 1 、e 1 、f 1 At least one of which is not selected from 0;
c is as described 1 、d 1 、g 1 、h 1 At least one is not selected from 0;
a is described 1 、b 1 、c 1 、d 1 At least one of which is not selected from 0;
said R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each occurrence, identically or differently, is selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted straight chain alkyl group of C1-C12, a substituted or unsubstituted branched chain alkyl group of C3-C12, a substituted or unsubstitutedOne of C3-C12 cycloalkyl and substituted or unsubstituted C3-C12 cycloalkenyl;
said R 1 、R 2 、R 5 、R 6 At least one of them is chosen from deuterium atoms;
said R 3 、R 4 、R 7 、R 8 At least one of them is chosen from deuterium atoms;
said R 1 、R 2 、R 3 、R 4 At least one of which is chosen from deuterium atoms;
m' is selected from 0,1, 2,3, 4 or 5;
each occurrence of R' is one of hydrogen atom, deuterium atom, substituted or unsubstituted C1-C12 linear alkyl, substituted or unsubstituted C3-C12 branched alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 cycloalkenyl and substituted or unsubstituted phenyl;
said L 1 、L 2 At each occurrence, the same or different is selected from one of a single bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group.
The invention also provides an organic electroluminescent device which comprises an anode, a cathode and an organic layer positioned between the anode and the cathode, wherein the organic layer comprises more than one of the aromatic amine compounds containing the phenylfluorene.
Preferably, the organic layer further comprises a triarylamine compound represented by formula (III):
Figure BDA0003714051230000022
wherein, Ar is 31 、Ar 32 Independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl and substituted or unsubstituted fluorenyl;
said L 30 Selected from substituted phenylene, substituted phenyleneOne of biphenyl groups, the substituents of which comprise at least one deuterium atom;
ar is 33 One selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted biphenyl;
a is described 31 Selected from 0,1, 2,3 or 4, said b 31 Selected from 0,1, 2 or 3;
said R 31 At each occurrence, the same or different one is selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopropane group, a substituted or unsubstituted cyclobutane group, a substituted or unsubstituted cyclopentanyl group, a substituted or unsubstituted cyclohexane group, a substituted or unsubstituted adamantyl group, and a substituted or unsubstituted norbornane group.
Has the advantages that:
the aromatic amine compound containing the phenylfluorene shown in the formula (I) has good hole mobility, can effectively improve the luminous efficiency of a device, reduces the energy consumption of the device, reduces the driving voltage, also has proper HOMO energy level and T1 value, and can achieve high energy level matching degree with an adjacent luminous layer and other organic functional layers when being used as a hole transmission functional layer, particularly a luminous auxiliary layer, so that the resistance of hole transmission is reduced, exciton can be reduced from the luminous layer to the hole transmission layer, the interface luminescence is avoided, the luminous efficiency of the device is further improved, and the driving voltage of the device is reduced; the aromatic amine compound containing the phenylfluorene introduces deuterium atoms at specific positions (on a condensed benzene ring of the phenylfluorene), and as the bonding strength between carbon and deuterium is higher than that between carbon and hydrogen, the aromatic amine compound not only can improve the thermal stability of the molecules, but also can increase the steric hindrance of the molecules, so that the arrangement among the molecules becomes excellent, and therefore, an OLED device is not easy to generate crystallization under the action of an electric field, the film forming stability of the material is further improved, and the service life of the device is further prolonged. Compared with the prior art, the aromatic amine compound containing the phenylfluorene shown in the formula (I) provided by the invention has a smaller deuterium atom ratio, and can reduce the production cost.
Detailed Description
The following will clearly and completely describe the technical solutions of the specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection 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 their natural isotopic abundance and unnatural abundance. In the case of hydrogen, all naturally occurring compounds contain about 0.0156 atomic% deuterium per hydrogen atom.
In the present invention, the use of "H" and "hydrogen atom" means that the hydrogen atom in the chemical structure contains no more than natural abundance of deuterium atoms or tritium atoms, e.g., no more than 0.0156 atomic% deuterium. "D" and "deuterium atoms" refer to deuterium content in abundance above natural abundance, e.g., any value in excess of 0.1 atomic%, in excess of 1 atomic%, in excess of 10 atomic%, e.g., where about 95 atomic% is deuterium.
The halogen atom in the present invention means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group in the present invention refers to a hydrocarbon group obtained by dropping one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group or a branched-chain alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but is not limited thereto; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, the isomeric form of n-pentyl, the isomeric form of n-hexyl, the isomeric form of n-heptyl, the isomeric form of n-octyl, the isomeric form of n-nonyl, the isomeric form of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
The cycloalkyl group in the present invention means a hydrocarbon group formed by removing one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 5 to 10 carbon atoms. Examples may include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, adamantyl, norbornyl, and the like. The cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, a 1-adamantyl group, a 2-adamantyl group or a norbornyl group.
The cycloalkenyl group in the present invention means a hydrocarbon group formed by dropping one hydrogen atom from a cycloolefin molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 5 to 10 carbon atoms. Examples may include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and the like, but are not limited thereto. The cycloalkyl group is preferably a cyclopentenyl group or a cyclohexenyl group.
The cycloalkynyl group in the present invention refers to a hydrocarbon group formed by dropping one hydrogen atom from a cycloalkyne molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 5 to 10 carbon atoms. Examples may include, but are not limited to, cyclopropynyl, cyclobutynyl, cyclopentynyl, cyclohexynyl, cycloheptynyl, and the like. The cycloalkyl group is preferably cyclopentynyl or cyclohexynyl.
The heterocyclic group in the present invention means a heterocyclic group in which one hydrogen atom is omitted from a heterocyclic molecule having at least one hetero atom in addition to carbon atoms as ring-constituting atoms, and the hetero atom includes a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom and the like, and preferably a nitrogen atom, an oxygen atom and a sulfur atom. Preferably 1 to 3 heteroatoms, more preferably 1 to 2 heteroatoms, and particularly preferably 1 heteroatom. Preferably 3 to 15 ring atoms, more preferably 3 to 12 ring atoms, and particularly preferably 5 to 6 ring atoms. Examples may include oxiranyl, thietanyl, propilidene, tetrahydropyrrolyl, piperidyl, morpholinyl, thiomorpholinyl, piperazinyl, and the like, but are not limited thereto. The heterocyclic group is preferably a tetrahydropyrrolyl group, a piperidyl group, a morpholinyl group, a thiomorpholinyl group or a piperazinyl group.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic compound molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the condensed ring aryl group refers to an aryl group having two or more aromatic rings in a molecule and condensed by sharing two adjacent carbon atoms with each other, and examples thereof include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, fluoranthenyl, spirobifluorenyl, and the like. The above aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a spirobifluorenyl group, a spiro-cyclopentyl-fluorenyl group, a spiro-cyclohexyl-fluorenyl group, a spiro-adamantyl-fluorenyl group, a spiro-cyclopentenyl-fluorenyl group, or a spiro-cyclohexenyl-fluorenyl group.
The heteroaryl group in the present invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group with a heteroatom, including but not limited to oxygen, sulfur, nitrogen or phosphorus atom, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, 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 pyridyl, pyrimidyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group or a phenoxathiyl group.
The condensed ring group formed by the aryl and the cycloalkyl refers to a group obtained by removing one hydrogen atom from one ring carbon atom of a condensed ring compound formed by sharing one carbon-carbon bond with an aromatic compound and a cycloalkane, and can be a monocyclic aryl group, a polycyclic aryl group or a group formed by a condensed ring aryl group and a 3-to 15-membered cycloalkyl group, preferably a group formed by a monocyclic aryl group and a 3-to 6-membered cycloalkyl group, more preferably a group formed by a phenyl group and cyclopentane or cyclohexane, and particularly preferably a group formed by a phenyl group and cyclopentane or cyclohexane. Examples include, but are not limited to, tetrahydronaphthyl, indanyl, and the like. Preferably, the bonding site in the condensed ring group formed by the aryl and the cycloalkyl can be on the aryl and also on the cycloalkyl; more preferably, the bonding site is on an aryl group.
The arylene group in the present invention means an aryl group having two bonding sites, that is, a divalent group. The description of aryl groups provided above can be applied with respect to it, except that the arylene group is a divalent group.
The heteroarylene group in the present invention means a heteroaryl group having two bonding sites, i.e., a divalent group. The description of heteroaryl provided above can be applied with respect to heteroarylene, except that heteroarylene is a divalent group.
The aryl group and cycloalkyl group-forming fused ring group described herein means a fused ring group having two bonding sites, that is, a divalent group. The description provided above for the fused ring group formed by an aryl group and a cycloalkyl group can be applied, except that the fused ring-anchoring group is a divalent group. Preferably, the two bonding sites in the fused ring-idene group formed by the aryl and cycloalkyl groups may be independently located on the aryl or cycloalkyl group, such as one located on the aryl group and the other located on the cycloalkyl group, or both located on the aryl group, or both located on the cycloalkyl group; more preferably, both of the bonding sites are located on an aryl group.
The "substitution" as referred to herein means that a hydrogen atom in some functional groups is replaced with another atom or functional group (i.e., substituent), and the substituted position is not limited as long as the position is a position at which a hydrogen atom is substituted, and when two or more are substituted, two or more substituents may be the same as or different from each other.
The "substituted or unsubstituted" as used herein means not substituted or substituted with one or more substituents selected from the group consisting of: deuterium atom, halogen atom, amino group, cyano group, nitro group, substituted or unsubstituted alkyl group of C1 to C30, substituted or unsubstituted cycloalkyl group of C3 to C30, substituted or unsubstituted cycloalkenyl group of C3 to C30, substituted or unsubstituted heterocyclic group of C3 to C30, substituted or unsubstituted alkoxy group of C1 to C30, substituted or unsubstituted aryl group of C6 to C60, substituted or unsubstituted aryloxy group of C6 to C60, substituted or unsubstituted heteroaryl group of C2 to C60, silyl group, preferably halogen atom, cyano group, nitro group, alkyl group of C1 to C12, cycloalkyl group of C3 to C12, cycloalkenyl group of C3 to C12, heterocyclic group of C3 to C12, aryl group of C6 to C30, heteroaryl group of C3 to C30, silyl group, in the case where a plurality of substituents are substituted, the same or different from each other; preferably, it means unsubstituted or substituted by one or more substituents selected from the group consisting of: deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, methyl group, trifluoromethyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopropane group, deuterium substituted cyclopropane group, methyl substituted cyclopropane group, ethyl substituted cyclopropane group, cyclobutane group, deuterium substituted cyclobutane group, methyl substituted cyclobutane group, ethyl substituted cyclobutane group, cyclopentyl group, deuterium substituted cyclopentyl group, methyl substituted cyclopentyl group, ethyl substituted cyclopentyl group, cyclohexyl group, deuterium substituted cyclohexyl group, methyl substituted cyclohexyl group, ethyl substituted cyclohexyl group, n-propyl substituted cyclohexyl group, n-butyl substituted cyclohexyl group, cyclohexane substituted cyclohexyl group, cycloheptyl group, cyclopentenyl group, deuterium substituted cyclopentenyl group, methyl substituted cyclopentenyl group, Ethyl-substituted cyclopentenyl, cyclohexenyl, cycloheptenyl, adamantyl, deuterium-substituted adamantyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, norbornyl, deuterium-substituted norbornyl, methyl-substituted norbornyl, ethyl-substituted norbornyl, tetrahydropyrrolyl, piperidinyl, morpholinyl, thiomorpholinyl, methyl-substituted piperazinyl, ethyl-substituted piperazinyl, phenyl-substituted piperazinyl, naphthyl-substituted piperazinyl, methoxy, ethoxy, phenyl, naphthyl, anthracenyl, phenanthryl, triphenylenyl, pyrenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, spirobifluorenyl, spiro-cyclopentyl-fluorenyl, spiro-cyclohexyl-fluorenyl, spiro-adamantyl-fluorenyl, spiro-cyclopentenyl-fluorenyl, spiro-adamantyl-fluorenyl, Spiro-cyclohexenyl-fluorenyl, pyridyl, pyrimidyl, triazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, N-phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, trimethylsilyl, triphenylsilyl, in the case of being substituted with a plurality of substituents, the plurality of substituents may be the same or different from each other.
In the present specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example, in the case of a liquid,
Figure BDA0003714051230000061
can represent
Figure BDA0003714051230000062
And so on.
The connection to form a ring structure according to the present invention means that the respective groups are connected to each other by chemical bonds, and optionally form double/triple bonds, and may constitute aromatic groups, as exemplified below:
Figure BDA0003714051230000063
the invention provides an aromatic amine compound containing phenylfluorene, which has a structure shown in a formula (I):
Figure BDA0003714051230000071
wherein, a is 1 、c 1 Each occurrence, identically or differently, is selected from 0,1, 2 or 3; b is 1 、d 1 Each occurrence, identically or differently, is selected from 0,1, 2,3 or 4; said e 1 、f 1 、g 1 、h 1 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4 or 5;
a is described 1 、b 1 、e 1 、f 1 At least one of which is not selected from 0;
c is as described 1 、d 1 、g 1 、h 1 At least one of which is not selected from 0;
a is as described 1 、b 1 、c 1 、d 1 At least one is not selected from 0;
said R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each occurrence, the same or different, is selected from the group consisting of a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C12 linear alkyl group, a substituted or unsubstituted C3-C12 branched alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, and a substituted or unsubstituted C3-C12 cycloalkenyl groupOne kind of (1);
said R 1 、R 2 、R 5 、R 6 At least one of them is chosen from deuterium atoms;
said R 3 、R 4 、R 7 、R 8 At least one of which is chosen from deuterium atoms;
said R 1 、R 2 、R 3 、R 4 At least one of which is chosen from deuterium atoms;
m' is selected from 0,1, 2,3, 4 or 5;
each occurrence of R' is one of hydrogen atom, deuterium atom, substituted or unsubstituted C1-C12 linear alkyl, substituted or unsubstituted C3-C12 branched alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 cycloalkenyl and substituted or unsubstituted phenyl;
said L 1 、L 2 At each occurrence, the same or different is selected from one of a single bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group.
Preferably, said substituent in "substituted or unsubstituted" is selected from deuterium atoms; an alkyl group of C1 to C12 substituted or unsubstituted with at least one member selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; C3-C12 cycloalkyl substituted or unsubstituted by at least one member selected from the group consisting of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; a cycloalkenyl group of C3 to C12 substituted or unsubstituted with one or more members selected from the group consisting of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; a heterocyclic group of C3-C12 substituted or unsubstituted with one or more members selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; aryl of C6-C30 substituted or unsubstituted by more than one of deuterium atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, biphenyl and deuterated biphenyl; a heteroaryl group of C3 to C30 substituted or unsubstituted with one or more members selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; the heterocyclic group or the heteroaryl group at least contains one of O, S, N, Si and Se, and the substituent is one or more, and when the substituent is a plurality of, the plurality of substituents are the same or different.
Preferably, said substituent in "substituted or unsubstituted" is selected from deuterium atoms; a methyl group; a deuterated methyl group; an ethyl group; a deuterated ethyl group; n-propyl; isopropyl group; n-butyl; sec-butyl; an isobutyl group; a tertiary butyl group; deuterated tert-butyl; a cyclopropyl group unsubstituted or substituted by one or more members selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; a cyclobutyl group substituted or unsubstituted by one or more members selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; a cyclopentyl group which is substituted or unsubstituted by more than one of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; a cyclohexane group which is unsubstituted or substituted by one or more members selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; a cyclopropenyl group which is unsubstituted or substituted by one or more members selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; cyclobutenyl which is substituted or unsubstituted by more than one of deuterium atom, tritium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; cyclopentenyl substituted or unsubstituted with one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; a cyclohexenyl group substituted or unsubstituted with one or more members of the group consisting of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; an adamantyl group substituted or unsubstituted with one or more members selected from the group consisting of a deuterium atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a phenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a biphenyl group and a deuterated biphenyl group; norbornyl which is unsubstituted or substituted with at least one member selected from the group consisting of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; phenyl unsubstituted or substituted by one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; naphthyl substituted or unsubstituted by more than one of deuterium atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, biphenyl and deuterated biphenyl; an anthracene group substituted or unsubstituted with one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; phenanthryl substituted or unsubstituted with one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; triphenylene substituted or unsubstituted with at least one of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; 9, 9-dimethylfluorenyl which is substituted or unsubstituted by one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; 9, 9-diphenylfluorenyl which is substituted or unsubstituted by more than one of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; spirobifluorenyl substituted or unsubstituted with one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; spiro-cyclopentyl-fluorenyl group which is substituted or unsubstituted by one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; spiro-cyclohexyl-fluorenyl substituted or unsubstituted with one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, deuterated biphenyl group; spiro-adamantyl-fluorenyl which is substituted or unsubstituted with one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; spiro-cyclopentenyl-fluorenyl group substituted or unsubstituted with one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, deuterated biphenyl group; spiro-cyclohexenyl-fluorenyl substituted or unsubstituted by one or more of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; carbazolyl which is substituted or unsubstituted by one or more members selected from the group consisting of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group and deuterated biphenyl group; dibenzofuranyl substituted or unsubstituted by at least one member selected from the group consisting of deuterium atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, phenyl group, deuterated phenyl group, naphthyl group, deuterated naphthyl group, biphenyl group, and deuterated biphenyl group; dibenzothienyl substituted or unsubstituted by more than one of deuterium atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, biphenyl and deuterated biphenyl; one of silyl groups which are substituted or unsubstituted by more than one of deuterium atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, tert-butyl groups, phenyl groups, deuterated phenyl groups, naphthyl groups, deuterated naphthyl groups, biphenyl groups and deuterated biphenyl groups, wherein the substituent group(s) is (are) one or more, and when the substituent group(s) is (are) more, the substituent groups are the same or different.
Preferably, the aromatic amine compound containing phenylfluorene has one of the structures shown in formula (II-A) or formula (II-B):
Figure BDA0003714051230000091
wherein, said m 1 ' is selected from 0,1, 2,3, 4 or 5; n is 1 ' is selected from 0,1, 2,3 or 4; said o is 1 ' is selected from 0,1, 2,3, 4 or 5;
said R 1 ' on each occurrence, the same or different groups are selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted straight-chain alkyl group of C1 to C12, a substituted or unsubstituted branched-chain alkyl group of C3 to C12, a substituted or unsubstituted cycloalkyl group of C3 to C12, a substituted or unsubstituted cyclic olefin of C3 to C12One of the groups;
a is described 1 、b 1 、c 1 、d 1 、e 1 、f 1 、g 1 、h 1 、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、L 1 、L 2 All as described above.
Preferably, R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each occurrence, the same or different, is one selected from the group consisting of a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopropane group, a substituted or unsubstituted cyclobutane group, a substituted or unsubstituted cyclopentanyl group, a substituted or unsubstituted cyclohexane group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornane group, a substituted or unsubstituted cyclopropenyl group, a substituted or unsubstituted cyclobutenyl group, a substituted or unsubstituted cyclopentenyl group, and a substituted or unsubstituted cyclohexenyl group.
Preferably, R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each occurrence, identically or differently, is selected from one of a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, a n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, a n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group, a deuterated tert-butyl group, or the structures shown below:
Figure BDA0003714051230000101
wherein, a is 11 At each occurrence, identically or differently selected from 0,1.2, 3,4 or 5; b is 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4,5, 6 or 7; c is as described 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4,5, 6,7,8 or 9; d is 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10 or 11; said e 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11, 12, 13, 14 or 15; f is 11 Each occurrence, identically or differently, is selected from 0,1, 2 or 3;
said R 11 Each occurrence, the same or different, is selected from the group consisting of hydrogen atom, deuterium atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, cyclopropyl, deuterated cyclopropyl, cyclobutyl, deuterated cyclobutyl, cyclopentyl, deuterated cyclopentyl, cyclohexyl, deuterated cyclohexyl, methyl-substituted cyclopentyl, ethyl-substituted cyclopentyl, methyl-substituted cyclohexyl, ethyl-substituted cyclohexyl, adamantyl, deuterated adamantyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, biphenyl, deuterated biphenyl, adamantyl-substituted phenyl, norbornyl-substituted phenyl, deuterated benzyl, and mixtures thereof, And the aryl group is one of adamantyl substituted biphenyl, norbornyl substituted biphenyl, tert-butyl substituted phenyl, tert-butyl substituted biphenyl, cyclopentyl substituted phenyl, cyclohexyl substituted phenyl, cyclopentyl substituted biphenyl and cyclohexyl substituted biphenyl.
Preferably, R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each occurrence, identically or differently, is selected from a hydrogen atom, a deuterium atom, or one of the structures shown below:
Figure BDA0003714051230000102
Figure BDA0003714051230000111
Figure BDA0003714051230000121
preferably, R is 1 ' at each occurrence, the same or different is selected from one of a hydrogen atom, a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopropane group, a substituted or unsubstituted cyclobutane group, a substituted or unsubstituted cyclopentanyl group, a substituted or unsubstituted cyclohexane group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornane group, a substituted or unsubstituted cyclopropenyl group, a substituted or unsubstituted cyclobutenyl group, a substituted or unsubstituted cyclopentenyl group, and a substituted or unsubstituted cyclohexenyl group.
Preferably, R is 1 ' on each occurrence, the same or different is selected from hydrogen atom, deuterium atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl, isopropyl, deuterated isopropyl, n-butyl, deuterated n-butyl, sec-butyl, deuterated sec-butyl, isobutyl, deuterated isobutyl, tert-butyl, deuterated tert-butyl, or one of the structures shown below:
Figure BDA0003714051230000131
wherein, a is 11 、b 11 、c 11 、d 11 、e 11 、f 11 、R 11 As described herein.
Preferably, R is 1 ' on each occurrence, the same or different is selected from a hydrogen atom, a deuterium atom, or one of the structures shown below:
Figure BDA0003714051230000132
Figure BDA0003714051230000141
Figure BDA0003714051230000151
preferably, said L 1 、L 2 At each occurrence, the same or different is selected from a single bond or one of the structures shown below:
Figure BDA0003714051230000152
wherein, a is 21 Each occurrence, identically or differently, is selected from 0,1, 2,3 or 4;
said R 21 Each occurrence, identically or differently, is selected from one of a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, a n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, a n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group, a deuterated tert-butyl group, or the structures shown below:
Figure BDA0003714051230000153
wherein, a is 11 、b 11 、c 11 、d 11 、e 11 、f 11 、R 11 As described in the present invention.
Preferably, R is 21 Each occurrence, which is the same or different, is selected from a hydrogen atom, a deuterium atom, or one of the structures shown below:
Figure BDA0003714051230000154
Figure BDA0003714051230000161
preferably, said L 1 、L 2 At each occurrence, the same or different is selected from a single bond or one of the structures shown below:
Figure BDA0003714051230000162
preferably, the
Figure BDA0003714051230000171
The same or different is selected from one of the structures shown below:
Figure BDA0003714051230000172
preferably, said a 1 、b 1 At least one is not selected from 0, c 1 、d 1 At least one of which is not selected from 0;
preferably, R is 1 、R 2 At least one of them is selected from deuterium atoms, said R 3 、R 4 At least one of them is chosen from deuterium atoms;
preferably, said
Figure BDA0003714051230000181
The same or different is selected from one of the structures shown below:
Figure BDA0003714051230000182
preferably, said
Figure BDA0003714051230000183
The same or different is selected from one of the structures shown below:
Figure BDA0003714051230000191
preferably, said
Figure BDA0003714051230000192
One selected from the structures shown below:
Figure BDA0003714051230000193
Figure BDA0003714051230000201
Figure BDA0003714051230000211
preferably, said
Figure BDA0003714051230000212
One selected from the structures shown below:
Figure BDA0003714051230000213
Figure BDA0003714051230000221
Figure BDA0003714051230000231
most preferably, the aromatic amine compound containing phenylfluorene is selected from one of the following compounds:
Figure BDA0003714051230000232
Figure BDA0003714051230000241
Figure BDA0003714051230000251
Figure BDA0003714051230000261
Figure BDA0003714051230000271
Figure BDA0003714051230000281
Figure BDA0003714051230000291
Figure BDA0003714051230000301
Figure BDA0003714051230000311
Figure BDA0003714051230000321
Figure BDA0003714051230000331
Figure BDA0003714051230000341
Figure BDA0003714051230000351
Figure BDA0003714051230000361
Figure BDA0003714051230000371
Figure BDA0003714051230000381
Figure BDA0003714051230000391
Figure BDA0003714051230000401
the aromatic amine compound containing phenylfluorene shown in formula (I) can be prepared by the following synthetic route:
Figure BDA0003714051230000402
wherein, X is 1 、X 2 Independently selected from chlorine atom, bromineAn atom or an iodine atom, said R 1 ～R 8 、R’、L 1 、L 2 、a 1 ～h 1 And m' are as defined in the present invention.
The above synthetic route employs the reaction types commonly used in organic synthesis, and the reaction conditions (for example, selection of the kind of reaction solvent, catalyst, ligand, base, etc., the amounts used, and the order and method of addition) are not particularly limited. The preparation method has the advantages of easily available raw materials, simple preparation process and excellent yield. The compound shown in formula (I) provided by the present invention can also be synthesized by using conventional reaction types in other organic synthesis, and the above is only an example of the synthetic route without particular limitation.
The invention also provides an organic electroluminescent device which comprises an anode, a cathode and an organic layer positioned between the anode and the cathode, wherein the organic layer comprises more than one of the aromatic amine compounds containing the phenylfluorene.
Preferably, the organic layer further comprises a triarylamine compound represented by formula (III):
Figure BDA0003714051230000411
wherein, Ar is 31 、Ar 32 Independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl and substituted or unsubstituted fluorenyl;
said L 30 One selected from substituted phenylene and substituted biphenylene, wherein the substituent group of the substituted biphenylene comprises at least one deuterium atom;
ar is 33 One selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted biphenyl;
a is described 31 Is selected from 0,1, 2,3 or 4, and the b31 is selected from 0,1, 2 or 3;
r is as described 31 Each timeWhen present, the same or different is one selected from deuterium atom, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted n-propyl group, substituted or unsubstituted isopropyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted sec-butyl group, substituted or unsubstituted isobutyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted cyclopropane group, substituted or unsubstituted cyclobutane group, substituted or unsubstituted cyclopentanyl group, substituted or unsubstituted cyclohexane group, substituted or unsubstituted adamantyl group, and substituted or unsubstituted norbornanyl group.
Preferably, Ar is 31 、Ar 32 Independently selected from one of the structures shown below:
Figure BDA0003714051230000412
Figure BDA0003714051230000421
Figure BDA0003714051230000431
Figure BDA0003714051230000441
preferably, Ar is 31 、Ar 32 Independently selected from one of the structures shown below:
Figure BDA0003714051230000442
Figure BDA0003714051230000451
Figure BDA0003714051230000461
Figure BDA0003714051230000471
Figure BDA0003714051230000481
Figure BDA0003714051230000491
preferably, said L 30 One selected from the structures shown below:
Figure BDA0003714051230000492
preferably, said L 30 One selected from the structures shown below:
Figure BDA0003714051230000493
preferably, Ar is 33 One selected from the structures shown below:
Figure BDA0003714051230000494
Figure BDA0003714051230000501
Figure BDA0003714051230000511
preferably, Ar is 33 Is selected from the group shown belowOne of the structures:
Figure BDA0003714051230000512
Figure BDA0003714051230000521
Figure BDA0003714051230000531
preferably, R is 31 Each occurrence, which is the same or different, is selected from the deuterium atom or one of the structures shown below:
Figure BDA0003714051230000532
Figure BDA0003714051230000541
preferably, R is 31 Each occurrence, identically or differently, is selected from a hydrogen atom, a deuterium atom, or one of the structures shown below:
Figure BDA0003714051230000542
preferably, the triarylamine compound shown in formula (III) is selected from one of the following compounds:
Figure BDA0003714051230000543
Figure BDA0003714051230000551
Figure BDA0003714051230000561
Figure BDA0003714051230000571
Figure BDA0003714051230000581
preferably, the organic layer includes a hole transport region, and the hole transport region includes one or more of the aromatic amine compounds containing a phenylfluorene according to the present invention.
Preferably, the hole transport region further comprises a triarylamine compound represented by formula (III).
Preferably, the hole transport region includes one or more of a hole injection layer, a hole transport layer, and a light emission auxiliary layer.
Preferably, the hole transport region comprises a hole injection layer and a hole transport layer; more preferably, one of the hole injection layer and the hole transport layer contains one or more of the aromatic amine compounds containing a phenylfluorene according to the present invention; more preferably, the hole injection layer and the hole transport layer each contain one or more kinds of the aromatic amine compound containing a phenylfluorene according to the present invention.
Preferably, the hole transport region comprises a hole injection layer, a hole transport layer and a light-emitting auxiliary layer; more preferably, one of the hole injection layer, the hole transport layer and the light-emission auxiliary layer contains one or more of the aromatic amine compounds containing a phenylfluorene according to the present invention; more preferably, the light-emission auxiliary layer contains at least one of the aromatic amine compounds containing a phenylfluorene according to the present invention.
Preferably, the hole transport region includes a hole injection layer, a hole transport layer, and a light emission auxiliary layer, the light emission auxiliary layer includes one or more kinds of the aromatic amine compounds containing phenylfluorene according to the present invention, and the hole transport layer includes one or more kinds of the triarylamine compounds represented by formula (III); more preferably, one of the hole injection layer and the hole transport layer contains one or more triarylamine compounds represented by formula (III); more preferably, the hole injection layer and the hole transport layer each contain one or more triarylamine compounds represented by formula (III).
Preferably, the organic layer further includes a light emitting layer and an electron transport region.
Preferably, the cathode further comprises a covering layer on the side facing away from the anode.
The hole injection layer of the present invention may have a single-layer structure composed of a single substance, or may have a single-layer structure or a multi-layer structure composed of different substances. Triarylamine compounds, porphyrin compounds, styrene compounds, polythiophene and its derivatives, phthalocyanine derivatives, allyl compounds, and other substances having high hole injection properties can be used, and examples thereof include 4,4',4 ″ -tris [ 2-naphthylphenylamino ] triphenylamine (2-TNATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN), copper phthalocyanine (CuPC), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanodimethyl-p-benzoquinone (F4-TCNQ), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT/PSS), aromatic amine compounds containing phenylfluorene according to the present invention, triarylamine compounds represented by formula (III), but is not limited thereto.
The hole transport layer of the present invention may have a single-layer structure composed of a single substance, or may have a single-layer structure or a multi-layer structure composed of different substances. Triarylamine compounds may be used, as may other hole mobilities at 10 -6 cm 2 Examples of the substance having a/Vs or higher include, but are not limited to, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (TDATA), an aromatic amine compound containing a phenylfluorene according to the present invention, and a triarylamine compound represented by formula (III). Preferably, theThe hole transport layer of (2) uses a triarylamine compound represented by formula (III).
The light-emitting auxiliary layer of the present invention may have a single-layer structure formed of a single substance, or may have a single-layer structure or a multi-layer structure formed of different substances. Triarylamine compounds, spirofluorene derivatives, dibenzofuran derivatives, or other materials with suitable HOMO and T1 energy levels may be used, examples of which include TPD, NPB, N4, N4-bis ([1,1 '-biphenyl ] -4-yl) -N4' -phenyl N4'- [1, 1': 4', 1' -terphenyl ] -4-yl- [1,1' -biphenyl ] -4,4' -diamine, N- ([1,1' -diphenyl ] -4-yl) -N- (9, 9-dimethyl-9H-furan-2-yl) -9,9' -spirobifluorene-2-amine, N-bis ([1,1' -biphenyl ] -4-yl) -3' - (dibenzo [ b, d ] furan-4-yl) - [1,1' -biphenyl ] -4-amine, the aromatic amine compound containing phenylfluorene described in the present invention, the triarylamine compound represented by formula (III), but not limited thereto. Preferably, the aromatic amine compound containing a phenylfluorene according to the present invention is used for the emission auxiliary layer.
The light-emitting layer of the present invention may contain only a guest material, or may be in a form in which a guest material is dispersed in a host material, and a dual host material may be formed using two host materials. As the guest material, a fluorescent compound such as a pyrene derivative, a fluoranthene derivative, an aromatic amine derivative and the like can be used, and examples thereof include 10- (2-benzothiazolyl) -2,3,6, 7-tetrahydro-1, 1,7, 7-tetramethyl-1H, 5H,11H- [ 1H]Benzopyran [6,7,8-ij]Quinolizin-11-one (C545T), 4' -bis (9-ethyl-3-carbazolenyl) -1,1' -biphenyl (BCzVBi), 4' -bis [4- (di-p-tolylamino) styryl]Examples of the phosphorescent material include biphenyl (DPAVBi), a metal complex such as an iridium complex, an osmium complex, and a platinum complex, and bis (4, 6-difluorophenylpyridine-N, C2) picolinatoiridium (FIrpic), tris (2-phenylpyridine) iridium (ir (ppy) 3 ) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) 2 (acac)) and the like. The host material is preferably a material having a higher LUMO and a lower HOMO than the guest material, for example, a metal complex such as an aluminum complex or a zinc complex, a heterocyclic compound such as an oxadiazole derivative or a benzimidazole derivative, or a condensed aromatic compound such as a carbazole derivative or an anthracene derivativeExamples of aromatic amine compounds such as triarylamine derivatives or condensed polycyclic aromatic amine derivatives include 8-hydroxyquinoline aluminum (Alq) 3 ) Bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1,1' -biphenyl-4-hydroxy) aluminum (BAlq), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), TPD, 4' -bis (9-Carbazole) Biphenyl (CBP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (2-naphthyl) Anthracene (ADN), but are not limited thereto.
The electron transport region comprises at least one of an electron injection layer, an electron transport layer and a hole blocking layer.
The electron injection layer can be a single-layer structure formed by a single substance, or a single-layer structure or a multi-layer structure formed by different substances, and one or more of the following substances can be selected: alkali metals, alkaline earth metals, alkali metal halides, alkaline earth metal halides, alkali metal oxides, alkaline earth metal oxides, alkali metal salts, alkaline earth metal salts, and other substances having a high electron-injecting property. Examples include 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, etc., but are not limited thereto.
The electron transport layer of the present invention may have a single-layer structure composed of a single substance, or a single-layer structure or a multilayer structure composed of different substances, and aluminum complexes, lithium complexes, beryllium complexes, zinc complexes, imidazole derivatives, benzimidazole derivatives, carbazole derivatives, phenanthroline derivatives, polymer compounds, and the like, which have high electron transport properties, may be used 3 8-hydroxyquinoline-lithium (Liq), bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (BeBq 2 ) 2, 9-bis (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (NBphen), BALq, 2- (4-biphenyl) -5-phenyl oxadiazole (PBD), and the like, but is not limited thereto.
The hole-blocking layer of the present invention may have a single-layer structure made of a single substance, or may have a single-layer structure or a multi-layer structure made of different substances. The selected material isThe T1 energy level is required to be higher than the light emitting layer so that the energy loss of the light emitting layer can be blocked. In addition, the HOMO energy level of the selected material is lower than that of the host material of the light-emitting layer, so that the hole blocking effect is achieved. Further, the electron mobility of the hole blocking layer material used is 10 -6 cm 2 and/Vs or above, the electron transmission is facilitated. One or more of the following may be selected: aluminum complexes, lithium complexes, beryllium complexes, oxazole derivatives, benzoxazole derivatives, thiazole derivatives, benzothiazole derivatives, imidazole derivatives, benzimidazole derivatives, phenanthroline derivatives, polymer compounds, and the like. Examples thereof include 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), and BALq.
Preferably, the organic layer comprises a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer;
preferably, the organic layer comprises a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer;
preferably, the organic layer comprises a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer and an electron injection layer;
preferably, the organic layer includes a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
The anode of the present invention may be a reflective anode, such as a reflective film formed of silver (Ag), magnesium (Mg), aluminum (Al), gold (Au), nickel (Ni), chromium (Cr), ytterbium (Yb) or an alloy thereof, or a transparent or semitransparent layer structure having a high work function, such as Indium Tin Oxide (ITO), indium zinc oxide (ZnO), Aluminum Zinc Oxide (AZO), Indium Gallium Oxide (IGO), indium oxide (In), or a transparent or semitransparent layer structure 2 O 3 ) Or tin oxide (SnO) 2 ) The layer structure formed depends on the type of device to be prepared, such as bottom emitting device (anode side emitting), transparent or semitransparent anode, top emitting device (cathode side emitting), and reverse emitting deviceAnd (4) emitting an anode.
The cathode can be a thin film with a low work function made of lithium, calcium, lithium fluoride/aluminum, silver, magnesium silver alloy and the like, and can be made into a reflecting electrode, a transparent electrode or a semitransparent electrode by adjusting the thickness of the film, wherein the reflecting cathode is required to be made if a bottom emitting device is required to be prepared, and the transparent or semitransparent cathode is required to be made if a top emitting device is required to be prepared.
The covering layer comprises a first covering layer and/or a second covering layer, and when the first covering layer or the second covering layer is included, the covering layer can be a single-layer structure formed by a single substance or a single-layer structure formed by different substances; when the first cover layer and the second cover layer are included, they are a multilayer structure made of a single substance or different substances. The cover material may be an organic or inorganic material, and may be, for example, a metal halide, an oxide, a nitride, an oxynitride, a sulfide, a selenide, an aromatic compound, a heteroaromatic compound, an arylamine compound, or the like, and examples thereof include LiF, CsF, MgF 2 、CaF 2 、CsCl、CuI、V 2 O 5 、WO 3 、MoO 3 、TiO 2 、ZrO、ZnO、SiO 2 、SiN、ZnS、Alq 3 The compound CP-1, the compound CP-2, the compound CP-3, the compound CP-4, the aromatic amine compound of the invention, but not limited thereto.
Figure BDA0003714051230000611
The organic layers, the cathode, the anode and the cover layer can be prepared by any one of vacuum evaporation, ink-jet printing, sputtering, plasma, ion plating, spin coating, dipping, screen printing and the like, and the film thickness of each layer is not particularly limited so as to obtain good device performance. The respective organic layers are preferably prepared by a method of vacuum evaporation, inkjet printing, or spin coating.
The thickness of each of the organic layer and the capping layer is usually 5nm to 100um, preferably 10nm to 200 nm. The thickness of the anode and the cathode is adjusted according to the required transparency.
The organic electroluminescent device provided by the invention can be applied to the fields of illumination, display and the like, and can be specifically listed as a display screen of a smart phone, a display screen of a tablet personal computer, a display screen of intelligent wearable equipment, a large-size display such as a television, VR (virtual reality), an automobile tail lamp and the like.
The technical scheme and technical effects of the present invention are further described below by examples and comparative examples.
The mass spectrum of the compound of the invention uses a G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer of Watts corporation of England, and chloroform is used as a solvent;
the elemental analysis was carried out by using a Vario EL cube type organic element analyzer of Elementar, Germany, and the sample mass was 5 to 10 mg.
Synthesis example 1: preparation of Compound 4
Figure BDA0003714051230000621
Synthesizing an intermediate C-4:
under the protection of nitrogen, raw material a-4(5.77g, 62.00mmol), raw material b-4(24.82g, 62.00mmol), Pd (OAc) are added into a reaction bottle in sequence 2 (0.21g，0.93mmol)、P(t-Bu) 3 (0.19g, 0.93mmol), sodium t-butoxide (10.57g, 110.00mmol), followed by addition of toluene (350mL), and the reaction was heated under reflux for 3.5 hours. After the reaction was terminated, the reaction mixture was cooled to room temperature, washed with dichloromethane and distilled water, and separated and extracted. The organic layer is dried by anhydrous magnesium sulfate, filtered, the filtrate is concentrated by reduced pressure distillation, recrystallized by ethyl acetate after cooling and suction filtration, and leached by suction filtration and rinsed by a small amount of ethyl acetate to obtain an intermediate C-4(20.72g, yield 81%), and the purity of the solid is not less than 99.53% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 412.2030 (theoretical value: 412.2019).
Synthesis of compound 4:
under the protection of nitrogen, the intermediate C-4(12.38g, 30.00mmol), the raw material C-4(10.71g, 30.00mmol) and Pd were added in sequence to a reaction flask 2 (dba) 3 (0.41g，0.45mmol)、X-Phos(021g, 0.45mmol), sodium t-butoxide (5.00g, 52.00mmol), then toluene (150mL) was added and the reaction was heated under reflux for 5 hours. After the reaction was terminated, the reaction mixture was cooled to room temperature, washed with dichloromethane and distilled water, and separated and extracted. The organic layer was dried over anhydrous magnesium sulfate, filtered to remove the solvent, recrystallized from toluene, and filtered by suction to give compound 4(17.15g, yield 78%) with a solid purity ≧ 99.89% by HPLC. Mass spectrum m/z: 732.3534 (theoretical value: 732.3522). Theoretical element content (%) C 56 H 32 D 7 N: c, 91.76; h, 6.32; n, 1.91. Measured elemental content (%): c, 91.78; h, 6.31; n, 1.88.
Synthetic example 2: preparation of Compound 59
Figure BDA0003714051230000622
According to the procedure of example 1, starting material a-4 was replaced with equimolar a-59 and starting material b-4 was replaced with equimolar b-59 to give compound 59(18.92g) having a solid purity of 99.93% or more as determined by HPLC. Mass spectrum m/z: 851.5202 (theoretical value: 851.5213). Theoretical element content (%) C 64 H 41 D 14 N: c, 90.20; h, 8.16; n, 1.64. Measured elemental content (%): c, 90.23; h, 8.18; n, 1.62.
Synthetic example 3: preparation of Compound 91
Figure BDA0003714051230000631
Synthesis of intermediate A-91:
under the protection of nitrogen, raw material c-4(16.42g, 46.00mmol), raw material d-91(13.20g, 46.00mmol), Pd (PPh) were added to the reaction flask in sequence 3 ) 4 (0.53g，0.46mmol)、K 2 CO 3 (9.54g, 69.00mmol), 240mL of toluene was added: ethanol: mixing water (2:1:1) and solvent, stirring the mixture, heating and refluxing for 2.5 hours. After the reaction was stopped, it was cooled to room temperature, toluene was added and the phases were separated, the toluene phase was washed three times with distilled water, dried over anhydrous magnesium sulfate and rotary evaporatedConcentrating the solvent, cooling, crystallizing, filtering, and mixing the obtained solid with toluene: ethanol ═ 20: 3 recrystallisation gave intermediate a-91(18.16g, 82% yield). The HPLC purity is more than or equal to 99.46 percent. Mass spectrum m/z: 480.1313 (theoretical value: 480.1329).
Synthesis of intermediate B-91:
under the protection of nitrogen, raw material b-4(32.43g, 81.00mmol), raw material d-91(23.25g, 81.00mmol), Pd (PPh) were added to the reaction flask in sequence 3 ) 4 (0.94g，0.81mmol)、K 2 CO 3 (16.59g, 120.00mmol), 400mL of toluene was added: ethanol: mixing water (2:1:1) and solvent, stirring the mixture, and heating and refluxing for reaction for 3 hours. After the reaction is stopped, cooling to room temperature, adding toluene, separating each phase, washing the toluene phase with distilled water for three times, drying with anhydrous magnesium sulfate, performing rotary evaporation and concentration on the solvent, cooling and crystallizing, performing suction filtration, and adding toluene to the obtained solid: ethanol ═ 10: 1 to yield intermediate B-91(32.30g, 83% yield). The HPLC purity is more than or equal to 99.39 percent. Mass spectrum m/z: 479.1274 (theoretical value: 479.1266).
Synthesis of intermediate C-91:
under the protection of nitrogen, the intermediate B-91(29.79g, 62.00mmol), the raw material a-4(5.77g, 62.00mmol), Pd (OAc) 2 (0.21g，0.93mmol)、P(t-Bu) 3 (0.19g, 0.93mmol), sodium t-butoxide (10.57g, 110.00mmol), 350mL of toluene was added, and the reaction was refluxed for 4 hours. After the reaction was terminated, the reaction mixture was cooled to room temperature, washed with dichloromethane and distilled water, and separated and extracted. The organic layer is dried by anhydrous magnesium sulfate, filtered, the filtrate is concentrated by reduced pressure distillation, recrystallized by ethyl acetate after cooling and suction filtration, and leached by suction filtration and rinsed by a small amount of ethyl acetate to obtain an intermediate C-91(24.44g, yield 80%), and the purity of solid is not less than 99.75% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 492.2568 (theoretical value: 492.2583).
Synthesis of compound 91:
under the protection of nitrogen, the intermediate C-91(14.78g, 30.00mmol), the intermediate A-91(14.44g, 30.00mmol) and Pd were added in sequence to a reaction flask 2 (dba) 3 (0.41g, 0.45mmol), X-Phos (0.21g, 0.45mmol), sodium tert-butoxide (5.00g, 52.00mmol) then added150mL of toluene was added, and the reaction was heated under reflux for 5 hours. After the reaction was terminated, the reaction mixture was cooled to room temperature, washed with dichloromethane and distilled water, and separated and extracted. The organic layer was dried over anhydrous magnesium sulfate, filtered to remove the solvent, recrystallized from toluene, and filtered by suction to give compound 91(19.29g, yield 72%) with a solid purity ≧ 99.95% by HPLC. Mass spectrum m/z: 892.4664 (theoretical value: 892.4650). Theoretical element content (%) C 68 H 32 D 15 N: c, 91.44; h, 6.99; n, 1.57. Measured elemental content (%): c, 91.41; h, 7.01; n, 1.56.
Synthetic example 4: preparation of Compound 119
Figure BDA0003714051230000641
Following the procedure of example 3, starting material d-91 was replaced with equimolar d-119 and intermediate A-91 was replaced with equimolar b-59 to afford compound 119(18.58g) having a solid purity of 99.91% or greater as determined by HPLC. Mass spectrum m/z: 814.4202 (theoretical value: 814.4211). Theoretical element content (%) C 62 H 30 D 13 N: c, 91.36; h, 6.92; n, 1.72. Measured elemental content (%): c, 91.33; h, 6.91; n, 1.74.
Synthesis example 5: preparation of Compound 123
Figure BDA0003714051230000642
According to the procedure of example 3, starting material b-4 was replaced with equimolar c-4, starting material d-91 was replaced with equimolar d-123 and intermediate A-91 was replaced with equimolar b-4 to give compound 123(19.12g) having a solid purity of 99.95% or more as determined by HPLC. Mass spectrum m/z: 884.4161 (theoretical value: 884.4148). Theoretical element content (%) C 68 H 40 D 7 N: c, 92.27; h, 6.15; n, 1.58. Measured elemental content (%): c, 92.30; h, 6.12; n, 1.56.
Synthetic example 6: preparation of Compound 185
Figure BDA0003714051230000643
Under the protection of nitrogen, raw material a-185(4.48g, 30.00mmol), raw material c-4(21.41g, 60.00mmol) and Pd were added in sequence to a reaction flask 2 (dba) 3 (0.41g, 0.45mmol), X-Phos (0.21g, 0.45mmol), and sodium tert-butoxide (7.21g, 75.00mmol), then 250mL of toluene was added, the mixture was stirred, and the reaction was heated under reflux for 4.5 hours. After the reaction, the reaction mixture was cooled to room temperature, washed with dichloromethane and distilled water, and separated and extracted. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed, and the obtained solid was recrystallized from toluene to obtain compound 185(18.25g, yield 77%) with a solid purity ≧ 99.90% by HPLC. Mass spectrum m/z: 789.4226 (theoretical value: 789.4211). Theoretical element content (%) C 60 H 39 D 8 N: c, 91.21; h, 7.01; n, 1.77. Measured elemental content (%): c, 91.19; h, 7.04; n, 1.79.
Synthetic example 7: preparation of Compound 203
Figure BDA0003714051230000651
Following the procedure of example 6, starting material a-185 was replaced with equimolar a-203 and starting material c-4 was replaced with equimolar b-4 to afford compound 203(17.47g) with a solid purity of 99.89% or more by HPLC. Mass spectrum m/z: 736.3786 (theoretical value: 736.3773). Theoretical element content (%) C 56 H 28 D 11 N: c, 91.26; h, 6.84; and N, 1.90. Measured elemental content (%): c, 91.22; h, 6.86; n, 1.93.
Synthesis example 8: preparation of Compound 247
Figure BDA0003714051230000652
Following the procedure of example 6, starting material a-185 was replaced with equimolar a-247 to afford compound 247(19.01g) having a solid purity of 99.91% or greater as determined by HPLC. Mass spectrum m/z: 867.4696 (theoretical value): 867.4680). Theoretical element content (%) C 66 H 45 D 8 N: c, 91.31; h, 7.08; n, 1.61. Measured elemental content (%): c, 91.33; h, 7.10; n, 1.59.
Synthetic example 9: preparation of Compound 259
Figure BDA0003714051230000653
Following the procedure of example 6, starting material a-185 was replaced with equimolar a-4 and starting material c-4 was replaced with equimolar b-4 to afford compound 259(17.13g) having a solid purity of 99.89% or more by HPLC. Mass spectrum m/z: 731.3446 (theoretical value: 731.3459). Theoretical element content (%) C 56 H 33 D 6 N: c, 91.89; h, 6.20; and N, 1.91. Measured elemental content (%): c, 91.86; h, 6.18; n, 1.93.
Synthetic example 10: preparation of Compound 260
Figure BDA0003714051230000654
Following the procedure of example 6, starting material a-185 was replaced with equimolar a-4 to afford compound 260(17.18g) having a solid purity of 99.92% or greater as determined by HPLC. Mass spectrum m/z: 733.3594 (theoretical value: 733.3585). Theoretical element content (%) C 56 H 31 D 8 N: c, 91.64; h, 6.45; and N, 1.91. Measured elemental content (%): c, 91.67; h, 6.43; n, 1.93.
Synthetic example 11: preparation of Compound 283
Figure BDA0003714051230000661
Synthesis of intermediate A-283:
under the protection of nitrogen, raw material c-4(27.12g, 76.00mmol), raw material d-119(21.51g, 76.00mmol) and Pd (PPh) are added into a reaction bottle in sequence 3 ) 4 (0.88g，0.76mmol)、K 2 CO 3 (15.76g, 114.00mmol) was added400mL of toluene: ethanol: mixing water (2:1:1) and solvent, stirring the mixture, and heating and refluxing for reaction for 3 hours. After the reaction is stopped, cooling to room temperature, adding toluene, separating each phase, washing the toluene phase with distilled water for three times, drying with anhydrous magnesium sulfate, performing rotary evaporation and concentration on the solvent, cooling and crystallizing, performing suction filtration, and adding toluene to the obtained solid: ethanol 10: 1 to yield intermediate A-283(31.57g, 87% yield). The HPLC purity is more than or equal to 99.41 percent. Mass spectrum m/z: 476.1089 (theoretical value: 476.1078).
Synthesis of Compound 283:
under the protection of nitrogen, raw material a-4(2.79g, 30.00mmol), intermediate A-283(28.65g, 60.00mmol) and Pd were added to a reaction flask in sequence 2 (dba) 3 (0.41g, 0.45mmol), X-Phos (0.21g, 0.45mmol), and sodium tert-butoxide (7.21g, 75.00mmol), then 250mL of toluene was added, the mixture was stirred, and the reaction was heated under reflux for 4.5 hours. After the reaction, the reaction mixture was cooled to room temperature, washed with dichloromethane and distilled water, and separated and extracted. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed, and the obtained solid was recrystallized from toluene to obtain compound 283(19.14g, yield 72%) having a purity of 99.95% or more by HPLC. Mass spectrum m/z: 885.4226 (theoretical value: 885.4211). Theoretical element content (%) C 68 H 39 D 8 N: c, 92.17; h, 6.25; n, 1.58. Measured elemental content (%): c, 92.18; h, 6.22; n, 1.61.
Synthetic example 12: preparation of Compound 312
Figure BDA0003714051230000662
According to the method of example 11, starting material c-4 was replaced with equimolar b-4, starting material d-119 was replaced with equimolar d-312 and intermediate A-283 was replaced with equimolar intermediate A-312 to give compound 312(19.10g) having a solid purity of 99.94% or more as determined by HPLC. Mass spectrum m/z: 883.4072 (theoretical value: 883.4085). Theoretical element content (%) C 68 H 41 D 6 N: c, 92.37; h, 6.04; n, 1.58. Measured elemental content (%): c, 92.40; h, 6.00; and N, 1.60.
Synthetic example 13: preparation of Compound 372
Figure BDA0003714051230000663
Following the procedure of example 1, starting material a-4 was replaced with equimolar a-372 to afford compound 372(18.45g) having a solid purity of 99.91% or greater as determined by HPLC. Mass spectrum m/z: 808.3824 (theoretical value: 808.3835). Theoretical element content (%) C 62 H 36 D 7 N: c, 92.04; h, 6.23; n, 1.73. Measured elemental content (%): c, 92.02; h, 6.26; n, 1.75.
Synthesis example 14: preparation of compound 386
Figure BDA0003714051230000671
Following the procedure of example 1, starting material a-4 was replaced with equimolar a-386 and starting material b-4 was replaced with equimolar b-59 to give compound 386(18.57g) with a solid purity of 99.92% or greater as determined by HPLC. Mass spectrum m/z: 824.4822 (theoretical value: 824.4839). Theoretical element content (%) C 62 H 20 D 23 N: c, 90.25; h, 8.06; and N, 1.70. Measured elemental content (%): c, 90.29; h, 8.04; n, 1.69.
Synthetic example 15: preparation of Compound 416
Figure BDA0003714051230000672
The procedure of example 1 was followed, substituting starting material a-4 for equimolar a-416 to give 416(19.35g) as a solid with a purity of 99.97% or more as determined by HPLC. Mass spectrum m/z: 920.5100 (theoretical value: 920.5087). Theoretical element content (%) C 70 H 52 D 7 N: c, 91.26; h, 7.22; n, 1.52. Measured elemental content (%): c, 91.28; h, 7.19; n, 1.54.
Synthetic example 16: preparation of Compound 436
Figure BDA0003714051230000673
According to the procedure of example 3, starting material b-4 was replaced with equimolar b-59, starting material d-91 was replaced with equimolar d-312, starting material a-4 was replaced with equimolar a-436 and intermediate A-91 was replaced with equimolar intermediate A-283 to give compound 436(19.75g) having a solid purity of 99.98% or more as determined by HPLC. Mass spectrum m/z: 967.4916 (theoretical value: 967.4900). Theoretical element content (%) C 74 H 37 D 14 N: c, 91.79; h, 6.76; and N is 1.45. Measured elemental content (%): c, 91.77; h, 6.79; n, 1.47.
Synthetic example 17: preparation of Compound 456
Figure BDA0003714051230000681
According to the procedure of example 1, starting material a-4 was replaced with equimolar a-456, starting material B-4 was replaced with equimolar B-59 and starting material c-4 was replaced with equimolar intermediate B-91 to give compound 456(19.18g) having a solid purity of 99.96% or more as determined by HPLC. Mass spectrum m/z: 899.5075 (theoretical value: 899.5089). Theoretical element content (%) C 68 H 25 D 22 N: c, 90.72; h, 7.72; n, 1.56. Measured elemental content (%): c, 90.74; h, 7.69; n, 1.59.
Synthetic example 18: preparation of Compound 468
Figure BDA0003714051230000682
Following the procedure of example 1, starting material a-4 was replaced with equimolar a-436 and starting material c-4 was replaced with equimolar intermediate A-283 to afford compound 468(19.12g) in a solid purity of 99.95% or greater as determined by HPLC. Mass spectrum m/z: 884.4160 theoretical value: 884.4148). Theoretical element content (%) C 68 H 40 D 7 N: c, 92.27; h, 6.15; n, 1.58. Measured elemental content (%): c, 92.30; h, 6.13; n, 1.56.
Synthetic example 19: preparation of compound 479
Figure BDA0003714051230000683
Following the procedure of example 1, intermediate C-4 was replaced with an equimolar amount of intermediate C-436 and starting material C-4 was replaced with an equimolar amount of intermediate B-119 to give compound 479(19.10g) having a solid purity of 99.96% or greater as determined by HPLC. Mass spectrum m/z: 883.4072 (theoretical value: 883.4085). Theoretical element content (%) C 68 H 41 D 6 N: c, 92.37; h, 6.04; n, 1.58. Measured elemental content (%): c, 92.36; h, 6.07; n, 1.59.
Synthesis example 20: preparation of Compound 499
Figure BDA0003714051230000684
Following the procedure of example 6, starting material a-185 was replaced with equimolar a-499 and starting material c-4 was replaced with equimolar b-4 to give compound 499(18.42g) with a solid purity of 99.91% or greater as determined by HPLC. Mass spectrum m/z: 807.3785 (theoretical value: 807.3772). Theoretical element content (%) C 62 H 37 D 6 N: c, 92.16; h, 6.11; n, 1.73. Measured elemental content (%): c, 92.20; h, 6.09; n, 1.72.
Synthetic example 21: preparation of Compound 506
Figure BDA0003714051230000691
Following the procedure of example 6, starting material a-185 was replaced with equimolar a-506 to afford compound 506(18.97g) having a solid purity of 99.93% or greater as determined by HPLC. Mass spectrum m/z: 865.4510 (theoretical value: 865.4524). Theoretical element content (%) C 66 H 43 D 8 N: c, 91.52; h, 6.86; n, 1.62. Measured elemental content (%): c, 91.54; h, 6.83; n, 1.65.
Synthetic example 22: preparation of Compound 525
Figure BDA0003714051230000692
According to the method of example 11, starting material c-4 was replaced with equimolar c-525, starting material D-119 was replaced with equimolar D-525, starting material a-4 was replaced with equimolar intermediate D-525, and intermediate A-283 was replaced with equimolar b-4 to give compound 525(19.49g) with a solid purity of 99.96% or more by HPLC. Mass spectrum m/z: 901.4565 (theoretical value: 901.4555). Theoretical element content (%) C 69 H 47 D 6 N: c, 91.86; h, 6.59; n, 1.55. Measured elemental content (%): c, 96.88; h, 6.62; n, 1.53.
Synthetic example 23: preparation of Compound 532
Figure BDA0003714051230000693
Following the procedure of example 6, starting material a-185 was replaced with equimolar a-372 and starting material c-4 was replaced with equimolar intermediate A-312 to afford compound 532(19.88g) with a solid purity of 99.98% or greater as determined by HPLC. Mass spectrum m/z: 959.4409 (theoretical value: 959.4398). Theoretical element content (%) C 74 H 45 D 6 N: c, 92.56; h, 5.98; n, 1.46. Measured elemental content (%): c, 92.58; h, 5.97; n, 1.43.
The organic materials in the device preparation examples are purified by sublimation, and the purity is over 99.99 percent. ITO glass substrates and ITO/Ag/ITO glass substrates used in the device production examples were commercially available.
The following are compounds used in device preparation examples in addition to the aromatic amine compound containing phenylfluorene according to the present invention:
Figure BDA0003714051230000701
test software, computer, K2400 digital Source Table (DIM) of Keithley, USAPR788 spectral scanning luminance meter of the company Photo Research in America forms a combined IVL test system, and the device prepared by the invention is tested under the conditions of atmospheric pressure and room temperature, wherein the current density of the device is 15mA/cm 2 Light emission efficiency, driving voltage, and the like. The lifetime (luminance decay to 95% of the initial luminance) of the devices prepared according to the invention was tested at atmospheric pressure and room temperature using the McScience M6000 OLED lifetime test system. The test results are shown in table 1.
Comparative device preparation example 1: comparison device 1
Firstly, the ITO/Ag/ITO glass substrate is ultrasonically cleaned for 20 minutes by deionized water for 2 times, then sequentially ultrasonically cleaned for 20 minutes by isopropanol, acetone and methanol, then exposed in ultraviolet rays and ozone for 30 minutes, and finally placed in a vacuum evaporation device for standby.
Evaporating the following layers on the ITO/Ag/ITO glass substrate layer by layer: a. HATCN is used as a hole injection layer and has the thickness of 10 nm; b. HT-124 is used as a hole transport layer and has the thickness of 100 nm; c. HTM-1 is used as a luminescence auxiliary layer and has the thickness of 30 nm; d. TBADN and BD (97: 3 by mass) as a light-emitting layer, and the thickness of the layer was 35 nm; e. TPBi is used as a hole blocking layer, and the thickness is 15 nm; e. NBphen and Liq (mass ratio of 5:2) are used as electron transport layers, and the thickness is 25 nm; f. LiF is used as an electron injection layer and has the thickness of 0.2 nm; g. mg and Ag (mass ratio of 1:6) are used as cathodes, and the thickness is 15 nm; h: CP-4 was used as a cap layer with a thickness of 80 nm.
Comparative device preparation examples 2 to 3: comparison device 2-3
And sequentially replacing the HTM-1 in the light-emitting auxiliary layer with HTM-2 and HTM-3, and obtaining the comparison devices 2-3 by the same steps as the comparison device preparation example 1.
Device preparation examples 1 to 23: light emitting device 1 to 23
The HTM-1 in the light-emitting auxiliary layer was sequentially replaced with the aromatic amine compound containing phenylfluorene of the present invention in synthesis examples 1 to 23, and the other steps were the same as in comparative device preparation example 1, to obtain devices 1 to 23.
Figure BDA0003714051230000702
Figure BDA0003714051230000711
The device data in table 1 show that the aromatic amine compound containing phenylfluorene is used as a light-emitting auxiliary layer, and the driving voltage and the light-emitting efficiency of the device are obviously improved, which indicates that the aromatic amine compound containing phenylfluorene is an OLED material with excellent performance and has good application prospect.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims (10)

1. An aromatic amine compound containing a phenylfluorene, characterized by having a structure represented by formula (I):
Figure FDA0003714051220000011
wherein, the a 1 、c 1 Each occurrence, identically or differently, is selected from 0,1, 2 or 3; b is 1 、d 1 Each occurrence, identically or differently, is selected from 0,1, 2,3 or 4; said e 1 、f 1 、g 1 、h 1 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4 or 5;
a is described 1 、b 1 、e 1 、f 1 At least one of which is not selected from 0;
c is as described 1 、d 1 、g 1 、h 1 At least one of which is not selected from 0;
a is described 1 、b 1 、c 1 、d 1 At least one of them is not selectedFrom 0;
said R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 At each occurrence, the same or different is selected from one of a hydrogen atom, a deuterium atom, a substituted or unsubstituted straight-chain alkyl group of C1 to C12, a substituted or unsubstituted branched-chain alkyl group of C3 to C12, a substituted or unsubstituted cycloalkyl group of C3 to C12, and a substituted or unsubstituted cycloalkenyl group of C3 to C12;
said R 1 、R 2 、R 5 、R 6 At least one of them is chosen from deuterium atoms;
said R 3 、R 4 、R 7 、R 8 At least one of them is chosen from deuterium atoms;
said R 1 、R 2 、R 3 、R 4 At least one of them is chosen from deuterium atoms;
m' is selected from 0,1, 2,3, 4 or 5;
each occurrence of R' is one of hydrogen atom, deuterium atom, substituted or unsubstituted C1-C12 linear alkyl, substituted or unsubstituted C3-C12 branched alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 cycloalkenyl and substituted or unsubstituted phenyl;
said L 1 、L 2 At each occurrence, the same or different is selected from one of a single bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group.
2. The aromatic amine compound containing phenylfluorene according to claim 1, wherein the aromatic amine compound containing phenylfluorene has one of the structures represented by formula (II-a) or formula (II-B):
Figure FDA0003714051220000012
wherein, said m 1 ' is selected from 0,1, 2,3, 4 or 5(ii) a N is 1 ' is selected from 0,1, 2,3 or 4; said o is 1 ' is selected from 0,1, 2,3, 4 or 5;
said R 1 ' at each occurrence, the same or different one selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted straight-chain alkyl group of C1 to C12, a substituted or unsubstituted branched-chain alkyl group of C3 to C12, a substituted or unsubstituted cycloalkyl group of C3 to C12, and a substituted or unsubstituted cycloalkenyl group of C3 to C12;
a is described 1 、b 1 、c 1 、d 1 、e 1 、f 1 、g 1 、h 1 、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、L 1 、L 2 Are as defined in claim 1.
3. The aromatic amine compound containing phenylfluorene according to claim 2, wherein R is 1 ' on each occurrence, the same or different is one selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopropylalkyl group, a substituted or unsubstituted cyclobutylalkyl group, a substituted or unsubstituted cyclopentylalkyl group, a substituted or unsubstituted cyclohexylalkyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornanyl group, a substituted or unsubstituted cyclopropenyl group, a substituted or unsubstituted cyclobutenyl group, a substituted or unsubstituted cyclopentenyl group, and a substituted or unsubstituted cyclohexenyl group.
4. The aromatic amine compound containing phenylfluorene according to claim 1, wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 On each occurrence, identically or differently, selected from deuterium atoms, substitutionsOr one of unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted cyclopropenyl, substituted or unsubstituted cyclobutenyl, substituted or unsubstituted cyclopentenyl, and substituted or unsubstituted cyclohexenyl;
said L 1 、L 2 At each occurrence, the same or different is selected from a single bond or one of the structures shown below:
Figure FDA0003714051220000021
wherein, a is 21 Each occurrence, identically or differently, is selected from 0,1, 2,3 or 4;
said R 21 Each occurrence, identically or differently, is selected from one of a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, a n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, a n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group, a deuterated tert-butyl group, or the structures shown below:
Figure FDA0003714051220000022
wherein, a is 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4 or 5; b is described 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4,5, 6 or 7; c is as described 11 At each occurrence, identically or differently selected from 0,1, 2,3, 4,5, 6,7,8 or9; d is mentioned 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10 or 11; said e 11 Each occurrence, identically or differently, is selected from 0,1, 2,3, 4,5, 6,7,8, 9,10, 11, 12, 13, 14 or 15; f is 11 Each occurrence, identically or differently, is selected from 0,1, 2 or 3;
said R 11 Each occurrence, identically or differently, is selected from the group consisting of a hydrogen atom, a deuterium atom, a methyl group, a deuterated methyl group, an ethyl group, a deuterated ethyl group, an n-propyl group, a deuterated n-propyl group, an isopropyl group, a deuterated isopropyl group, an n-butyl group, a deuterated n-butyl group, a sec-butyl group, a deuterated sec-butyl group, an isobutyl group, a deuterated isobutyl group, a tert-butyl group, a deuterated tert-butyl group, a cyclopropane group, a deuterated cyclopropane group, a cyclobutane group, a deuterated cyclobutane group, a cyclopentane group, a deuterated cyclopentane group, a cyclohexane group, a deuterated cyclohexane group, a methyl-substituted cyclopentane group, an ethyl-substituted cyclohexane group, an adamantyl group, a deuterated adamantyl group, a methyl-substituted adamantyl group, an ethyl-substituted adamantyl group, a phenyl group, a deuterated naphthyl group, a biphenyl group, a deuterated biphenyl group, an adamantyl-substituted phenyl group, a norbornyl-substituted phenyl group, a, And the aryl group is one of adamantyl substituted biphenyl, norbornyl substituted biphenyl, tert-butyl substituted phenyl, tert-butyl substituted biphenyl, cyclopentyl substituted phenyl, cyclohexyl substituted phenyl, cyclopentyl substituted biphenyl and cyclohexyl substituted biphenyl.
5. The aromatic amine compound containing phenylfluorene according to claim 1, wherein the aromatic amine compound is a compound represented by formula (I)
Figure FDA0003714051220000031
Figure FDA0003714051220000032
The same or different is selected from one of the structures shown below:
Figure FDA0003714051220000033
Figure FDA0003714051220000041
6. the aromatic amine compound containing phenylfluorene according to claim 1, wherein a is 1 、b 1 At least one is not selected from 0, c 1 、d 1 At least one of which is not selected from 0;
said R 1 、R 2 At least one of them being chosen from deuterium atoms, said R being 3 、R 4 At least one of them is chosen from deuterium atoms.
7. The aromatic amine compound containing phenylfluorene according to claim 1, wherein the aromatic amine compound containing phenylfluorene is selected from one of the following structures:
Figure FDA0003714051220000042
Figure FDA0003714051220000051
Figure FDA0003714051220000061
Figure FDA0003714051220000071
Figure FDA0003714051220000081
Figure FDA0003714051220000091
Figure FDA0003714051220000101
Figure FDA0003714051220000111
Figure FDA0003714051220000121
Figure FDA0003714051220000131
Figure FDA0003714051220000141
Figure FDA0003714051220000151
Figure FDA0003714051220000161
Figure FDA0003714051220000171
Figure FDA0003714051220000181
Figure FDA0003714051220000191
Figure FDA0003714051220000201
Figure FDA0003714051220000211
8. an organic electroluminescent device comprising an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises at least one aromatic amine compound containing phenylfluorene according to any one of claims 1 to 7.
9. The organic electroluminescent device of claim 8, wherein the organic layer further comprises a triarylamine compound represented by formula (III):
Figure FDA0003714051220000221
wherein, Ar is 31 、Ar 32 Independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl and substituted or unsubstituted fluorenyl;
said L 30 One selected from the group consisting of a substituted or unsubstituted phenylene group substituted with at least one deuterium atom, a substituted or unsubstituted biphenylene group substituted with at least one deuterium atom;
ar is 33 Is selected fromOne of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted biphenyl;
a is described 31 Selected from 0,1, 2,3 or 4, said b 31 Selected from 0,1, 2 or 3;
said R 31 At each occurrence, the same or different one is selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted cyclopropane group, a substituted or unsubstituted cyclobutane group, a substituted or unsubstituted cyclopentanyl group, a substituted or unsubstituted cyclohexane group, a substituted or unsubstituted adamantyl group, and a substituted or unsubstituted norbornane group.
10. The organic electroluminescent device according to claim 9, wherein the organic layer comprises a hole transport region comprising a hole injection layer, a hole transport layer and a light-emitting auxiliary layer, wherein the light-emitting auxiliary layer comprises one or more of the aromatic amine compounds containing phenylfluorene according to any one of claims 1 to 7, and the hole transport layer comprises one or more of the triarylamine compounds represented by formula (III) according to claim 9.
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