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CN117126190A - Triarylamine derivative and organic electroluminescent device thereof - Google Patents

Triarylamine derivative and organic electroluminescent device thereof Download PDF

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Publication number
CN117126190A
CN117126190A CN202311068896.2A CN202311068896A CN117126190A CN 117126190 A CN117126190 A CN 117126190A CN 202311068896 A CN202311068896 A CN 202311068896A CN 117126190 A CN117126190 A CN 117126190A
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equimolar
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刘喜庆
韩春雪
周雯庭
孙敬
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Changchun Hyperions Technology Co Ltd
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Changchun Hyperions Technology Co Ltd
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Abstract

The invention provides a triarylamine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. The invention mainly solves the problems of the existing majority of hole transport materials that the performance is not ideal enough, the luminous efficiency of the organic electroluminescent device is low, the service life is short, and the like. The triarylamine derivative shown in the formula 1 is connected with the groups containing C, si and Ge through the 1,4 positions, so that the carrier transmission efficiency is improved, higher hole transmission efficiency is obtained, the triarylamine derivative is applied to a hole transmission layer, the luminous efficiency of a device can be improved, the service life of the device can be prolonged, and the durability of the device is improved. The triarylamine derivative and the organic electroluminescent device thereof provided by the invention can be widely applied to the technical field of information display, such as mobile phones, tablet computers, televisions, wearable equipment, VR, vehicle displays, vehicle taillights and the like.

Description

Triarylamine derivative and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a triarylamine derivative and an organic electroluminescent device thereof.
Background
In recent years, organic semiconductor materials are one of the most active directions in the material field, and compared with inorganic semiconductor materials, the organic semiconductor materials have the advantages of good solubility, high transparency, easy processing, fast photoelectric response, potential biocompatibility and the like, and are increasingly important in the application in the high and new technical fields of photoelectric conversion, photovoltaic cells and the like. The OLEDs (Organic Light Emitting Diode) organic electroluminescent device has the remarkable characteristics of simple structure, high response speed, active luminescence, light weight, thinness, luminescent color diversity, wide viewing angle, low energy consumption and the like, has obvious advantages in the fields of display and illumination, and is widely focused on technical application, scientific research and the like.
With the development of materials of various functional layers of OLEDs, materials with various properties are continuously emerging, and in order to adapt to the diversity of materials, the structure of the devices is continuously optimized. According to the number of organic functional layers, the device structure is simply divided into a single-layer device, a double-layer device, a three-layer device and a multi-layer device, most of the current OLEDs devices mostly adopt a multi-layer sandwich type double-carrier direct current injection type device, and the device is generally composed of an anode Indium Tin Oxide (ITO) with a high work function, a metal cathode with a low work function and an organic functional layer, wherein the organic functional layer mainly comprises a Hole Transport Layer (HTL), an emitting layer (EML) and an Electron Transport Layer (ETL). Under the action of an externally applied electric field, electrons and holes generated by the cathode and the anode are injected into the middle organic film layer, the injected electrons and holes migrate to the light-emitting layer in the electron transmission layer and the hole transmission layer, remain in the light-emitting layer to the greatest extent, increase the recombination opportunity, form excitons, the excitons transition back to the ground state in a radiation mode, and a light-emitting phenomenon is generated, namely, electroluminescence is generated, and the energy level from the excited state to the ground state determines the light-emitting color.
The hole transport layer which is one of the most important functional layers in the OLEDs has the basic functions of improving the transport efficiency of holes in the device, effectively blocking electrons in the light-emitting layer and realizing the maximum recombination of carriers; meanwhile, the energy barrier of holes in the injection process is reduced, and the injection efficiency of the holes is improved, so that the brightness, the efficiency and the service life of the device are improved. Therefore, the excellent hole transport material should have good film forming property, good thermal stability, and appropriate HOMO orbital energy level to ensure efficient injection and transport of holes between the electrode and the organic functional layer, and should also have high hole mobility. Therefore, it is an urgent need to develop a hole transport material having a suitable HOMO orbital energy level and a high hole mobility, and to improve the thermal stability and film forming property of the material by adjusting the structure of the material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a triarylamine derivative and an organic electroluminescent device thereof.
The invention provides a triarylamine derivative, which has a general formula shown in a structural formula 1,
wherein the Ar is 1 Selected from the group represented by formula a or formula b,
The X is selected from C, si and Ge, and the Ra and Rb are independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C2-C30 heteroaryl; the R is 3 、R 4 Independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 aliphatic ring, and fused ring group of C6-C30 aromatic ring; said n 3 Selected from 0, 1, 2 or 3; said n 4 Selected from 0, 1, 2, 3 or 4;
the Ar is as follows 2 A substituted or unsubstituted C6 to C30 aryl or a substituted or unsubstituted C2 to C30 heteroaryl;
the Ar is as follows 3 Selected from the group consisting of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
the R is 1 、R 2 Independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C60 aliphatic ring, and C6-C30 aryl One of the condensed ring groups of the aromatic ring, or optionally two adjacent R 1 Bonded together to form a substituted or unsubstituted cyclic structure, or optionally two adjacent R' s 2 Bonded together to form a substituted or unsubstituted cyclic structure; said n 1 Selected from 0, 1, 2, 3 or 4; said n 2 Selected from 0, 1, 2, 3 or 4;
the L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group.
The invention also provides an organic electroluminescent device, which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or outside one or more than one of the anode and the cathode, and the organic layer contains the triarylamine derivative.
The beneficial effects are that:
the invention discloses a triarylamine derivative shown in a formula 1 and an organic electroluminescent device thereof, wherein the triarylamine derivative is connected with groups containing elements such as C, si, ge and the like through 1,4 positions, so that the triarylamine derivative has better hole transmission performance and electron blocking performance, and when the triarylamine derivative is used in the organic electroluminescent device, the device has better photoelectric performance, and is particularly characterized by higher luminous efficiency, longer service life and the like.
Detailed Description
The present application is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are meant to be illustrative of the application and not limiting the scope of the application, and that modifications of the application, which are all equivalent to those skilled in the art to which the application pertains, are within the scope of the application as claimed.
In the compounds of the present application, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance.
Examples of the halogen according to the present application may include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The term "C1-C15" in the "substituted or unsubstituted C1-C15 alkyl" as used herein refers to the number of carbon atoms in the unsubstituted "alkyl" and does not include the number of carbon atoms in the substituent. The term "C6-C30" in the "substituted or unsubstituted C6-C30 aryl" refers to the number of carbon atoms in the unsubstituted "aryl" and does not include the number of carbon atoms in the substituent. And so on.
The alkyl refers to a monovalent group formed by removing one hydrogen atom in an alkane molecule. The number of carbon atoms of the alkyl group is from C1 to C15, preferably from C1 to C10. Examples of such alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl and the like.
The chain alkyl group having more than three carbon atoms according to the present invention includes isomers thereof, for example, propyl group includes n-propyl group, isopropyl group, butyl group includes n-butyl group, sec-butyl group, isobutyl group, tert-butyl group. And so on.
The cycloalkyl refers to a monovalent group formed by removing one hydrogen atom in a cycloparaffin molecule. The cycloalkyl group has 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, bornyl, norbornyl, fenchyl, isobornyl, and the like.
The aryl refers to a monovalent group formed by removing one hydrogen atom from the aromatic nucleus carbon of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl groups, polycyclic aryl groups, and condensed ring aryl groups. The number of carbon atoms of the aryl group is from C6 to C30, preferably from C6 to C20, more preferably from C6 to C15, and still more preferably from C6 to C12. Examples of the aryl group include, but are not limited to, phenyl, biphenyl, terphenyl, tetrabiphenyl, pentacenyl, naphthyl, indenyl, indanyl, dihydronaphthyl, tetrahydronaphthyl, phenanthryl, triphenylenyl, anthracenyl, pyrenyl, fluorenyl, spirobifluorenyl, spiroanthracenyl, benzofluorenyl, benzospirobifluorenyl, and the like.
Heteroaryl as used herein refers to a monovalent group in which at least one of the aromatic nucleus carbon atoms in the aryl group is replaced with a heteroatom. The heteroaryl group has a carbon number of from C2 to C30, preferably from C2 to C15, and more preferably from C2 to C10. Such heteroatoms include, but are not limited to, atoms as described below, O, S, N, si, B, P, and the like. The heteroaryl group includes monocyclic heteroaryl, fused ring heteroaryl. Examples of heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, furanyl, benzofuranyl, dibenzofuranyl, benzodibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, benzodibenzothienyl, carbazolyl, and the like.
As used herein, "substituted or unsubstituted silyl" refers to-Si (R) k ) 3 A group wherein each R k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkenyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, fused ring groups of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic ring, fused ring groups of substituted or unsubstituted C3-C30 alicyclic and C2-C60 heteroaromatic ring. Preferably, each R k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl. The number of carbon atoms of the alkyl group is preferably 1 to 20, preferably 1 to 15, more preferably 1 to 10, and most preferably 1 to 8. The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, preferably 3 to 15, more preferably 3 to 10, and most preferably 3 to 7. The number of carbon atoms of the aryl group is preferably 6 to 20, preferably 6 to 13, more preferably 6 to 12, and most preferably 6 to 10. Preferably, each R k The same or different groups are selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstitutedUnsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl. The "alkylsilyl" refers to silyl (-SiH) 3 ) At least one substituent R of (2) k Is an alkyl group, and preferred alkylsilyl groups include, but are not limited to, trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl; the term "arylsilyl" refers to silyl (-SiH) 3 ) At least one substituent R of (2) k The aryl group is preferably an arylsilyl group, and specifically includes triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, and the like, but is not limited thereto.
The arylene group refers to a divalent group formed by removing two hydrogen atoms from an aromatic nucleus carbon in an aromatic hydrocarbon molecule. The arylene group has a carbon number of from C6 to C30, preferably from C6 to C20, and more preferably from C6 to C10. The arylene group includes a monocyclic arylene group, a polycyclic arylene group, a fused ring arylene group, or a combination thereof. Examples of the arylene group include, but are not limited to, phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, triphenylene, perylene, pyrenylene, indenylene, fluorenylene, benzofluorenylene, dibenzofluorenylene, spirobifluorenylene, benzospirobifluorenylene, and the like.
Heteroaryl-ene as used herein refers to a divalent group in which at least one carbon atom of the arylene group is replaced with a heteroatom. The heteroarylene group has a carbon number of from 2 to 30, preferably from 2 to 20, and more preferably from 2 to 10. Such heteroatoms include, but are not limited to, the atoms shown below, O, S, N, si, B, P, and the like. The heteroarylene includes a monocyclic heteroarylene, a polycyclic heteroarylene, a fused ring heteroarylene, or a combination thereof. Examples of heteroarylene groups include, but are not limited to, a pyridyl group, a pyrimidylene group, a quinolyl group, an isoquinolyl group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a benzodibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, a benzodibenzothienyl group, and the like.
The condensed ring group of the aliphatic ring and the aromatic ring according to the present invention means a ring having one or more aromatic rings and having one or more aliphatic rings condensed with each other by sharing two adjacent carbon atoms in the molecule, the aromatic ring is preferably 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, most preferably 6 to 12 carbon atoms, the aliphatic ring is preferably 3 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, most preferably 3 to 7 carbon atoms, and examples include benzocyclopropane group, benzocyclobutane group, benzocyclopentene group, benzocyclohexenyl group, benzocycloheptene group, naphthocyclopropane group, naphthocyclobutane group, naphthocyclopentane group, naphthocyclohexenyl group, naphthocyclopentene group, naphthocyclohexenyl group, etc., but are not limited thereto.
The term "unsubstituted" in the term "substituted or unsubstituted" as used herein means that a hydrogen atom on a group is not replaced with any substituent, and "substituted" means that at least one hydrogen atom on a group is replaced with a substituent, and when a plurality of hydrogens are replaced with a plurality of substituents, the plurality of substituents may be the same or different, and the position of the hydrogen replaced with the substituent may be any position.
The substituent group represented by "substituent" in the above "substituted or unsubstituted" is selected from one of deuterium group, halogen, cyano group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C6-C60 aryl group, substituted or unsubstituted C2-C60 heteroaryl group, substituted or unsubstituted benzoaliphatic hydrocarbon ring group. For example, a group such as deuterium, halogen atom, cyano group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, adamantyl group, camphene group, norbornyl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylene group, pyrenyl group, fluorenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, benzofluorenyl group, dibenzofluorenyl group, spirodibenzofluorenyl group, dibenzofuranyl group, benzodibenzofuranyl group, dibenzothiophenyl group, benzodibenzothiophenyl group, benzocyclopropane group, benzocyclobutanyl group, indanyl group, tetrahydronaphthyl group, benzocycloheptyl group, benzocyclooctalkyl group, indenyl group, dihydronaphthyl group and the like is preferable, but the above substituent may be unsubstituted, partially substituted or completely substituted with deuterium.
In this specification, when a substituent is not fixed in position on a ring, it is meant that it can be attached to any of the corresponding selectable positions of the ring. For example, the number of the cells to be processed,can indicate-> Can representCan representAnd so on.
In the present invention, "adjacent two groups are bonded to form a substituted or unsubstituted cyclic structure" means that a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle is formed by bonding adjacent groups to each other and optionally aromatizing. The hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. The heterocycle may include aliphatic or aromatic heterocycles. The aliphatic hydrocarbon ring may be a saturated aliphatic hydrocarbon ring or an unsaturated aliphatic hydrocarbon ring, and the aliphatic heterocyclic ring may be a saturated aliphatic heterocyclic ring or an unsaturated aliphatic heterocyclic ring. The hydrocarbon ring and the heterocyclic ring may be a single ring or a polycyclic group. In addition, a ring formed by bonding adjacent groups may be linked to another ring to form a spiro structure. As exemplified below:
in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, such as benzene, naphthalene, phenanthrene, triphenylene, cyclopentane, cyclohexane, cyclopentene, cyclohexene, fluorene, pyridine, pyrimidine, dibenzofuran, dibenzothiophene, but is not limited thereto.
The invention provides a triarylamine derivative, which has a structural general formula shown in a formula 1,
wherein the Ar is 1 Selected from the group represented by formula a or formula b,
the X is selected from C, si and Ge, and the Ra and Rb are independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C2-C30 heteroaryl; the R is 3 、R 4 Independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 aliphatic ring and fused ring group of C6-C30 aromatic ringThe method comprises the steps of carrying out a first treatment on the surface of the Said n 3 Selected from 0, 1, 2 or 3; said n 4 Selected from 0, 1, 2, 3 or 4;
the Ar is as follows 2 A substituted or unsubstituted C6 to C30 aryl or a substituted or unsubstituted C2 to C30 heteroaryl;
the Ar is as follows 3 Selected from the group consisting of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
The R is 1 、R 2 Independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C60 aliphatic ring and fused ring group of C6-C30 aromatic ring, or optionally adjacent two R 1 Bonded together to form a substituted or unsubstituted cyclic structure, or optionally two adjacent R' s 2 Bonded together to form a substituted or unsubstituted cyclic structure; said n 1 Selected from 0, 1, 2, 3 or 4; said n 2 Selected from 0, 1, 2, 3 or 4;
the L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group.
Preferably, said R 1 、R 2 Independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinoxalinyl, and substituted or unsubstituted quinazolinyl; or optionally adjacent two R is a number of 1 Bonded together to form a substituted or unsubstituted benzene ring, or optionally two adjacent R' s 2 Bonded together to form a substituted or unsubstituted benzene ring.
Preferably, the Ar 1 One selected from the group consisting of:
the Ra, R is b Independently selected from the group consisting of substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl-substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinoxalinyl, and substituted or unsubstituted quinazolinyl;
the R is 3 、R 4 Independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted nonyl, substituted or unsubstituted decyl, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted phenyldimethylsilyl, substituted or unsubstituted diphenylmethylsilyl, substituted or unsubstituted dimethylethylsilyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted camphyl, substituted or unsubstituted norbornyl, substituted or unsubstituted benzocyclopropane One of an alkyl group, a substituted or unsubstituted benzocyclobutanyl group, a substituted or unsubstituted benzocyclopentanyl group, a substituted or unsubstituted benzocyclohexenyl group, a substituted or unsubstituted benzocycloheptane group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dihydronaphthyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group; in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other; said n 3 Selected from 0, 1, 2 or 3; said n 4 Selected from 0, 1, 2, 3 or 4.
Further preferably, the Ar 1 One selected from the group consisting of:
the R is 3 、R 4 Independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted Substituted octyl, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted camphenethyl, substituted or unsubstituted norbornyl, substituted or unsubstituted benzocyclopropanyl, substituted or unsubstituted benzocyclobutanyl, substituted or unsubstituted benzocyclopentanyl, substituted or unsubstituted benzocyclohexenyl, substituted or unsubstituted benzocycloheptane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other;
The R is 5 The same or different is selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted camphene, substituted or unsubstitutedSubstituted or unsubstituted benzocyclopropane, substituted or unsubstituted benzocyclobutane, substituted or unsubstituted benzocyclopentane, substituted or unsubstituted benzocyclohexane, substituted or unsubstituted benzocycloheptane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other;
Said n 3 Selected from 0, 1, 2 or 3; said n 4 Selected from 0, 1, 2, 3 or 4; said n 5 Selected from 0, 1, 2, 3, 4 or 5; said n 6 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; said n 7 Selected from 0, 1, 2, 3, 4, 5 or 6.
Preferably, the Ar 2 One selected from the group consisting of:
wherein the R is f One selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 aliphatic ring and C6-C30 aromatic ring fused ring group;
said f 1 Selected from 0, 1, 2, 3, 4 or 5;
said f 2 Selected from 0, 1, 2, 3 or 4;
said f 3 Selected from 0, 1, 2 or 3;
said f 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7;
said f 5 Selected from 0, 1, 2, 3, 4, 5 or 6;
said f 6 Selected from 0, 1 or 2;
the "×" indicates the binding site to an adjacent atom.
Further preferably, said R f Selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, deuterated methyl or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, trimethylsilyl, triphenylsilyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, pyridinyl, pyrimidinyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, halogen, trifluoromethyl, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, pyridyl, pyrimidinyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other.
Preferably, the Ar 3 One selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinoxalinyl group, and a substituted or unsubstituted quinazolinyl group.
Further preferably, the Ar 3 One selected from the group consisting of:
wherein the R is g One or more selected from deuterium, cyano, halogen, trifluoromethyl, deuterated methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other;
said g 1 Selected from 0, 1, 2, 3, 4 or 5;
said g 2 Selected from 0, 1, 2, 3 or 4;
said g 3 Selected from 0, 1, 2 or 3;
said g 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7;
said g 5 Selected from 0, 1, 2, 3, 4, 5 or 6.
Preferably, the L 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted pyridylene group, or a substituted or unsubstituted pyrimidinylene group.
Further preferably, the L 1 、L 2 、L 3 Independently selected from a single bond or one of the following groups:
most preferably, the triarylamine derivative represented by structural formula 1 is selected from one of the structures shown below,
the specific chemical structures of the triarylamine derivative of formula 1 of the present invention are listed above, but the present invention is not limited to these chemical structures, and any substituent groups defined above are included on the basis of the triarylamine derivative of formula 1.
Further, the invention also provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer is positioned between the anode and the cathode or positioned at the outer side of one or more than one of the anode and the cathode, and the organic layer contains the triarylamine derivative shown in the formula 1.
Preferably, the organic layer comprises a hole transport region comprising the triarylamine derivative of the present invention.
Preferably, the hole transport region comprises at least one of a hole injection layer and a hole transport layer, the hole transport layer is positioned between the hole injection layer and the cathode, and at least one of the hole injection layer and the hole transport layer contains the triarylamine derivative of the present invention.
Preferably, the hole transport region comprises a hole transport layer comprising the triarylamine derivative of the present invention.
Preferably, the hole transport layer comprises a first hole transport layer, a second hole transport layer and a third hole transport layer, the second hole transport layer is located between the first hole transport layer and the cathode, the third hole transport layer is located between the second hole transport layer and the cathode, and at least one of the first hole transport layer, the second hole transport layer and the third hole transport layer contains the triarylamine derivative.
Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer is positioned between the first hole transport layer and the cathode, and the second hole transport layer contains the triarylamine derivative of the present invention.
Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer is positioned between the first hole transport layer and the cathode, and the first hole transport layer contains the triarylamine derivative of the present invention.
Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer is positioned between the first hole transport layer and the cathode, and the first hole transport layer and the second hole transport layer contain the triarylamine derivative.
The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.
The material of each layer of thin film in the organic electroluminescent device is not particularly limited, and materials known in the art can be used. The organic layer of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device are described below:
the anode of the present invention may be made of a conductor with a high work function to aid hole injection. The material for the anode of the present invention may comprise: metals or alloys thereof, metal oxides, laminates, conductive polymers, combinations of metals and oxides, and the like, for example, nickel (Ni), platinum (Pt), vanadium (V), silver (Ag), gold (Au), zinc oxide (ZnO), indium Tin Oxide (ITO), indium Zinc Oxide (IZO), indium oxide (In 2O 3), indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO), polypyrrole, polyaniline, zinc oxide: aluminum (ZnO: al), and the like. But is not limited thereto.
The cathode of the present invention may be made of a conductor having a high work function to aid hole injection. The material for the cathode of the present invention may comprise: metals or alloys thereof, multilayer structural materials, and the like, for example, silver (Ag), aluminum (Al), magnesium (Mg), tin (Sb), magnesium silver (Mg: ag), calcium/magnesium (Ca/Mg), and the like. But is not limited thereto.
The hole injection material according to the present invention is preferably a material capable of reducing the interface barrier between the anode and the hole transport layer. Materials described below, polycyano conjugated organic compounds, alkylene compounds, phthalocyanine metal complexes, aromatic amine derivatives, polymers, and the like. Specific examples may include 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl p-benzoquinone (F) 4 -TCNQ), 2' - (cyclopropane-1, 2, 3-tridecyl) -tris (2-perfluorophenyl acetonitrile), copper phthalocyanine (CuPC), N 4 ,N 4 '- (biphenyl-4, 4' -diacyl) bis (N) 4 ,N 4 ',N 4 '-triphenylbiphenyl-4.4' -diamine) (TPT 1 ) N, N-phenyl-N, N- (9-phenyl-3-carbazolyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) (PEDOT)/poly (styrenesulfonic acid) (PSS), and the like, but is not limited thereto.
The hole transport material is preferably a material with better hole transport capacity and better stability. As described below, aromatic amine derivatives, carbazole derivatives, polymers, and the like. Specific examples may include N- ([ 1,1' -biphenyl ] -4-yl) -N- (4- (dibenzo [ b, d ] furan-4-yl) phenyl) dibenzo [ b, d ] furan-4-amine, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), N4-bis ([ 1,1' -biphenyl ] -4-yl) -N4' - ([ 1,1':4',1 "-terphenyl ] -4-yl) -N4' -phenyl- [1,1' -biphenyl ] -4,4' -diamine, N ' -tetrabiphenyl diamine, 9' -diphenyl-6- (9-phenyl-9H-carbazol-3-yl) -9H, 4',4" -tris (carbazol-9-yl) triphenylamine (TCTA), p-phenylene ethylene (PPV), and the like, but are not limited thereto. The triarylamine derivative represented by formula 1 of the present invention is preferred.
The light-emitting layer according to the present invention may contain only a guest material, or may take the form of a guest material dispersed in a host material, wherein the host material may be composed of one or more materials.
As the host material of the light emitting layer of the present invention, there may be included a condensed aromatic ring derivative, a heterocyclic compound, etc., such as 9, 10-bis (2-naphthyl) Anthracene (ADN), 10 '-bis (biphenyl-4-yl) -9,9' -dianthracene (BANE), 1,3, 5-tris (pyren-1-yl) benzene (TPB 3), 1,3, 5-tris (carbazole-9-yl) benzene (TCP), 14,4',4 "-tris (carbazole-9-yl) triphenylamine (TCTA), 4' -bis (carbazole-9-yl) -2,2 '-dimethylbiphenyl (CDBP), 4' -bis (carbazole-9-yl) biphenyl (CBP), etc., but not limited thereto.
As the light emitting layer guest material of the present invention, an aromatic amine derivative, a condensed aromatic ring derivative, a heterocyclic derivative, a metal complex, or the like, for example, 4 '-bis (4- (9H-carbazol-9-yl) styryl) biphenyl (BSB 4), 4' -bis [4- (diphenylamino) styryl ] biphenyl (BDAVBi), 10 '-bis (3, 5-bis (trifluoromethyl) phenyl) -9,9' -dianthracene (Ban- (3, 5) -CF 3), 5,6,11, 12-tetraphenyltetracene (Rubrene), coumarin 545T (C-525T) tris (2-phenyl-3-methyl-pyridine) iridium (Ir (3 mppy) 3), bis (2- (naphthalen-2-yl) pyridine) (acetylacetonate) iridium (III) (Ir (npy) 2 acac), tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3), or the like may be included, but is not limited thereto.
The hole blocking layer material of the present invention needs to have a good hole blocking capability in order to block holes in the light emitting layer. As described below, imidazole derivatives, phenanthroline derivatives, metal complexes, triazine derivatives, and the like. Specific examples may include 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 2- (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (hnben), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1, 1' -biphenyl-4-hydroxy) aluminum (BAlq), 2- (9, 9-dimethyl-9H-fluoren-2-yl) 4- (9, 9-diphenyl-9H-fluoren-4-yl) -6-phenyl-1, 3, 5-triazine, and the like, but are not limited thereto.
The electron transport layer material is preferably a material with better electron transport capability and better stability. As described below, imidazole derivatives, phenanthroline derivatives, pyridine derivatives, triazine derivatives, quinoline derivatives, oxadiazole derivatives, triazole derivatives, metal complexes and the like. Specific examples may include 2- (4- (9, 10-bis (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 2- (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (HNBEN), 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 3'- [5' - [3- (3-pyridinyl) phenyl ] (TmPyPB), 1, 4-bis (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) naphthalene 2- (3- (phenanthren-9-yl) -5- (pyridin-3-yl) phenyl) -4, 6-diphenyl-1, 3, 5-triazine, 1,3, 5-tris (4- (pyridin-4-yl) quinolin-2-yl) benzene (TPyQB), 2, 5-bis- (4-naphthyl) -1,3, 4-oxadiazole (BND), 3- (biphenyl-4-yl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), lithium 8-hydroxyquinolinate (LiQ), and the like, but is not limited thereto.
The electron blocking layer according to the present invention preferably uses a material having a difference in absolute value from the HOMO value of the hole transport layer of 0.07eV or more and 0.35eV or less, and specific examples may include triarylamine derivatives, spirofluorene derivatives, furan derivatives, and the like, such as TPD, NPB, N, 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, and the like, but is not limited thereto.
The electron injection layer material according to the present invention is preferably a material capable of reducing the interface barrier between the cathode and the electron transport layer. Materials, metals, metal compounds, metal oxides, and the like, as described below, but are not limited thereto. Specific examples may include magnesium (Mg), rubidium (Rb), lithium fluoride (LiF), 8-hydroxyquinoline-lithium, etc. (LiQ), rubidium fluoride (RbF), cesium carbonate (Cs) 2 CO 3 ) Lithium boron oxide (LiBO) 2 ) Molybdenum oxide (MoO) 3 ) Alumina (Al) 2 O 3 ) Vanadium oxide (V) 2 O 5 ) Etc., but is not limited thereto.
The material for the cover layer according to the present invention is preferably a material capable of improving the luminous efficiency of the device. The following materials, metal compounds, aromatic amine derivatives, carbazole derivatives, and the like, but are not limited thereto. Specific examples may include tris (8-hydroxyquinoline) aluminum (III) (Alq 3), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4' -bis (9-carbazole) biphenyl (abbreviated CBP), and the like, but are not limited thereto.
The method for producing the thin films of each layer in the organic electroluminescent device of the present invention is not particularly limited, and vacuum deposition, sputtering, spin coating, spray coating, screen printing, laser transfer, etc. may be used, but are not limited thereto.
The organic electroluminescent device is mainly applied to the technical field of information display, and is widely applied to various information displays in the aspect of information display, such as a tablet personal computer, a flat television, a mobile phone, a smart watch, a digital camera, VR, a vehicle-mounted system, wearable equipment and the like.
Synthetic examples
Raw materials and reagents: the starting materials or reagents used in the following synthetic examples are not particularly limited and may be commercially available products or prepared by methods well known to those skilled in the art. The raw materials and the reagents used in the invention are all reagent pure.
Instrument: g2—si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); vario EL cube organic element analyzer (Elementar, germany).
The method for producing the triarylamine derivative of formula 1 of the present invention is not particularly limited, and conventional methods known to those skilled in the art can be employed. For example, a carbon-nitrogen coupling reaction, a carbon-carbon coupling reaction, etc., for example, the triarylamine derivative of structural formula 1 of the present invention can be prepared by using the synthetic route shown below.
The X is 1 、X 2 、X 3 Halogen atoms, which may be the same or different, are selected from the group consisting of halogen atoms, I, br, cl, as described below, for example.
Synthetic examples
Synthesis example 1: preparation of intermediate c-34:
under the protection of nitrogen, n-34 (25.70 g,80.00 mmol), m-34 (12.83 g,80.00 mmol), pd (PPh 3 ) 4 (0.92 g,0.80 mmol) and K 2 CO 3 (22.11 g,160.00 mmol) was added to a mixed solvent of 480mL of toluene, 160mL of ethanol and 160mL of water, and the mixture was stirred and the mixed solution of the above reactants was heated under reflux for 7h. After the reaction, cooling to room temperature, adding distilled water, extracting with dichloromethane, standing for liquid separation, collecting an organic layer, drying with anhydrous magnesium sulfate, filtering, concentrating the filtrate by reduced pressure distillation, cooling for crystallization, suction-filtering, and recrystallizing the obtained solid with toluene/methanol (volume ratio of 8:1) to obtain an intermediate c-34 (22.84 g, yield of 80%), wherein the purity of the solid is not less than 99.83% by HPLC detection. Mass spectrum m/z:356.1259 (theory: 356.1270).
The raw materials are correspondingly replaced, and the intermediate c can be prepared according to the preparation method of the intermediate c-34, wherein the raw materials are shown in the following table:
synthesis example 2: preparation of intermediate c-525
Under argon, a' -525 (43.00 g,110.00 mmol) was suspended in 900mL diethyl ether and then cooled at-30-40 ℃. 96.8mL of a 2.5M hexane solution of n-butyllithium was slowly added dropwise to the solution at the same temperature, and after the completion of the dropwise addition, the mixture was stirred for 5 hours. Then, a diethyl ether solution (20.05 g,115.50 mmol) of b' -525 was added dropwise at-30℃to-40℃and the mixture was stirred at the same temperature for 8 hours, and then allowed to warm to room temperature. After the reaction was completed, water was added, extraction was performed with methylene chloride, the organic phases were combined, washed with water, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the residue was washed with 800mL of heptane to obtain intermediate c-525 (15.05 g, yield 41%); HPLC purity. Mass spectrum m/z:333.9426 (theory: 333.9412).
The raw materials are correspondingly replaced, and the intermediate c can be prepared according to the preparation method of the intermediate c-525, wherein the raw materials are shown in the following table:
synthesis example 3: preparation of intermediate c-602
B' -602 (40.13 g,150.00 mmol) was dissolved in 750mL THF under Ar and then cooled to-78 ℃. 112.50mL (180.00 mmol/1.6M in hexane) of n-BuLi are added dropwise at-78℃and the mixture is stirred at the same temperatureMix for 60 minutes. Then, a solution of a' -602 (47.39 g,180.00 mmol) in diethyl ether (500 mL) was added dropwise at-78℃and the mixture was stirred at the same temperature for 5 hours, and then allowed to warm to room temperature. After completion of the reaction, NH was used 4 The mixture was quenched with saturated aqueous Cl. After extraction with diethyl ether (3X 300 mL), the solution was subjected to MgSO 4 Drying, filtering, and evaporating to dryness. The residue was washed with 1000mL of heptane to give intermediate M-602 (49.24 g, 79% yield); HPLC purity. Mass spectrum m/z:416.0399 (theory: 416.0387).
Tetrabutylammonium iodide (35.46 g,110.00 mmol) and t-butyl hydroperoxide solution (66 mL/5.5M in decane, 3.65 mmol) were added to a solution of M-602 (45.70 g,110.00 mmol) in toluene (800 mL). After stirring at room temperature for 10 minutes, the mixture was heated to 90 ℃, stirred at that temperature for 30 hours and cooled to room temperature. After filtration through a short silica pad eluting with methylene chloride (2.8L), the residue was purified by fractional column chromatography to give intermediate c-602 (17.74 g, 39% yield); HPLC purity. Mass spectrum m/z:414.0217 (theory: 414.0231).
Synthesis example 4: preparation of Compound 10
Preparation of intermediate B-10:
under nitrogen, a-10 (29.10 g,60.00 mmol), b-10 (5.59 g,60.00 mmol), naOt-Bu (10.09 g,105.00 mmol) were dissolved in 525ml toluene and Pd was added under stirring 2 (dba) 3 (0.27 g,0.30 mmol) and X-Phos (0.29 g,0.60 mmol), and the mixture of the above-mentioned reactants was heated under reflux for 8 hours. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The solid obtained was recrystallized from toluene/methanol (volume ratio 10:1) to give intermediate B-10 (23.73 g, 73% yield) with purity of > 99.87% by HPLC. Mass spectrum m/z:541.2779 (theory: 541.2770).
Preparation of compound 10:
under nitrogen, B-10 (21.67 g,40.00 mmol), c-10 (16.54 g,40.00 mmol), naOt-Bu (6.92 g,72.00 mmol) were dissolved in 325ml toluene and Pd (OAc) was added under stirring 2 (0.13g,0.60mmol)、P(t-Bu) 3 (1.2 mL/0.5M in toluene, 0.60 mmol) and the mixture of the above reactants was heated under reflux for 9h. After the reaction was completed, cooled to room temperature, water was added, extraction was performed with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The solid obtained was recrystallized from toluene to give compound 10 (22.73 g, yield 65%), the purity of the solid was ≡ 99.92% by HPLC. Mass spectrum m/z:873.3779 (theory: 873.3791). Theoretical element content (%) C 65 H 51 NSi: c,89.30; h,5.88; n,1.60. Measured element content (%): c,89.27; h,5.93; n,1.58.
Synthesis example 5: preparation of Compound 27
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-27 and c-10 was replaced with equimolar c-27 to obtain Compound 27 (19.71 g), and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:693.2839 (theory: 693.2852). Theoretical element content (%) C 51 H 39 NSi: c,88.27; h,5.66; n,2.02. Measured element content (%): c,88.24; h,5.70; n,2.05.
Synthesis example 6: preparation of Compound 34
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-27, b-10 was replaced with equimolar b-34, and c-10 was replaced with equimolar c-34 to obtain compound 34 (19.39 g), and the purity of the solid was ≡ 99.97% by HPLC. Mass spectrum m/z:663.3272 (theory: 663.3259). Theoretical element content (%) C 48 H 37 D 4 NSi:C,86.83; h,6.83; n,2.11. Measured element content (%): c,86.78; h,6.79; n,2.08.
Synthesis example 7: preparation of Compound 48
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-48, b-10 was replaced with equimolar b-48, and c-10 was replaced with equimolar c-48 to obtain Compound 48 (20.46 g), and the purity of the solid was ≡ 99.94% by HPLC. Mass spectrum m/z:751.3621 (theory: 751.3634). Theoretical element content (%) C 55 H 49 NSi: c,87.84; h,6.57; n,1.86. Measured element content (%): c,87.79; h,6.61; n,1.88.
Synthesis example 8: preparation of Compound 60
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-60 and c-10 was replaced with equimolar c-60 to obtain Compound 60 (20.05 g), and the purity of the solid was ≡ 99.98% by HPLC. Mass spectrum m/z:770.3105 (theory: 770.3117). Theoretical element content (%) C 56 H 42 N 2 Si: c,87.23; h,5.49; n,3.63. Measured element content (%): c,87.20; h,5.53; n,3.59.
Synthesis example 9: preparation of Compound 75
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-10, b-10 was replaced with equimolar b-75, and c-10 was replaced with equimolar c-48 to give Compound 75 (19.96 g), and the purity of the solid was ≡ 99.93% by HPLC detection. Mass spectrum m/z:817.3179 (theory: 817.3165). Theoretical element content (%) C 61 H 43 NSi: c,89.56; h,5.30; n,1.71. Measured element content (%): c,89.58; h,5.26; n,1.68.
Synthesis example 10: preparation of Compound 89
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-48, b-10 was replaced with equimolar b-89, and c-10 was replaced with equimolar c-48 to obtain Compound 89 (19.68 g), and the purity of the solid was ≡ 99.96% by HPLC. Mass spectrum m/z:702.3431 (theory: 702.3417). Theoretical element content (%) C 51 H 30 D 9 NSi: c,87.13; h,6.88; n,1.99. Measured element content (%): c,87.11; h,6.92; n,1.96.
Synthesis example 11: preparation of Compound 96
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-48, b-10 was replaced with equimolar b-96, and c-10 was replaced with equimolar c-48 to obtain compound 96 (20.70 g), and the purity of the solid was ≡ 99.91% by HPLC detection. Mass spectrum m/z:749.3490 (theory: 749.3478). Theoretical element content (%) C 55 H 47 NSi: c,88.07; h,6.32; n,1.87. Measured element content (%): c,88.09; h,6.29; n,1.91.
Synthesis example 12: preparation of Compound 98
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-98, and c-10 was replaced with equimolar c-98 to give compound 98 (19.71 g), and the purity of the solid was ≡ 99.93% by HPLC detection. Mass spectrum m/z:820.3262 (theoretical value:820.3274). Theoretical element content (%) C 60 H 44 N 2 Si: c,87.77; h,5.40; n,3.41. Measured element content (%): c,87.80; h,5.36; n,3.44.
Synthesis example 13: preparation of Compound 104
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-104, and c-10 was replaced with equimolar c-104, to obtain compound 104 (19.51 g), and the purity of the solid was ≡ 99.92% by HPLC detection. Mass spectrum m/z:773.3431 (theory: 773.3416). Theoretical element content (%) C 57 H 39 D 4 NSi: c,88.44; h,6.12; n,1.81. Measured element content (%): c,88.39; h,6.08; n,1.78.
Synthesis example 14: preparation of Compound 107
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-48, b-10 was replaced with equimolar b-107, and c-10 was replaced with equimolar c-48 to obtain compound 107 (20.02 g), and the purity of the solid was ≡ 99.97% by HPLC. Mass spectrum m/z:769.3153 (theory: 769.3165). Theoretical element content (%) C 57 H 43 NSi: c,88.91; h,5.63; n,1.82. Measured element content (%): c,88.86; h,5.59; n,1.85.
Synthesis example 15: preparation of Compound 128
Following the same procedure as in Synthesis example 4 substituting a-10 with equimolar a-48, b-10 with equimolar b-128 and c-10 with equimolar c-128, compound 128 (19) was obtained.77g) HPLC detection of solid purity ∈ 99.95%. Mass spectrum m/z:809.3491 (theory: 809.3478). Theoretical element content (%) C 60 H 47 NSi: c,88.96; h,5.85; n,1.73. Measured element content (%): c,88.94; h,5.88; n,1.69.
Synthesis example 16: preparation of Compound 146
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-27, b-10 was replaced with equimolar b-146 and c-10 was replaced with equimolar c-48 to obtain compound 146 (20.60 g), and the purity of the solid was not less than 99.98% as measured by HPLC. Mass spectrum m/z:857.3492 (theory: 857.3478). Theoretical element content (%) C 64 H 47 NSi: c,89.57; h,5.52; n,1.63. Measured element content (%): c,89.62; h,5.48; n,1.60.
Synthesis example 17: preparation of Compound 169
The same preparation method as in Synthesis example 4 was followed except that a-10 was replaced with equimolar a-169, b-10 was replaced with equimolar b-169, and c-10 was replaced with equimolar a-169 to obtain compound 169 (23.56 g), and the purity of the solid was ≡ 99.96% by HPLC detection. Mass spectrum m/z:997.3548 (theory: 997.3560). Theoretical element content (%) C 73 H 51 NSi 2 : c,87.82; h,5.15; n,1.40. Measured element content (%): c,87.77; h,5.19; n,1.38.
Synthesis example 18: preparation of Compound 180
Following the same procedure as in Synthesis example 4, a-10 was replaced with equimolar c-48 and b-10 was replaced with equimolar c-48b-180, c-10 was replaced with equimolar a-169 to give compound 180 (20.64 g), solid purity ≡99.91% by HPLC. Mass spectrum m/z:831.2970 (theory: 831.2957). Theoretical element content (%) C 61 H 41 NOSi: c,88.05; h,4.97; n,1.68. Measured element content (%): c,88.10; h,4.93; n,1.72.
Synthesis example 19: preparation of Compound 187
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-48, b-10 was replaced with equimolar b-187, and c-10 was replaced with equimolar c-128 to obtain compound 187 (20.01 g), and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:757.2819 (theory: 757.2801). Theoretical element content (%) C 55 H 39 NOSi: c,87.15; h,5.19; n,1.85. Measured element content (%): c,87.20; h,5.22; n,1.81.
Synthesis example 20: preparation of Compound 202
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-48, b-10 was replaced with equimolar b-202, and c-10 was replaced with equimolar c-48, to obtain compound 202 (20.62 g), and the purity of the solid was ≡ 99.94% by HPLC. Mass spectrum m/z:858.3416 (theory: 858.3430). Theoretical element content (%) C 63 H 46 N 2 Si: c,88.07; h,5.40; n,3.26. Measured element content (%): c,88.12; h,5.37; n,3.30.
Synthesis example 21: preparation of Compound 221
The same preparation method as in Synthesis example 4Substitution of a-10 for equimolar a-221, b-10 for equimolar b-221, and c-10 for equimolar c-221 gave compound 221 (19.94 g), which was found to have a solid purity of > 99.97% by HPLC. Mass spectrum m/z:655.3253 (theory: 655.3239). Theoretical element content (%) C 50 H 41 N: c,91.56; h,6.30; n,2.14. Measured element content (%): c,91.59; h,6.27; n,2.16.
Synthesis example 22: preparation of Compound 268
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-268, and c-10 was replaced with equimolar c-268 to give compound 268 (20.75 g), and the purity of the solid was ≡ 99.94% by HPLC detection. Mass spectrum m/z:740.4161 (theory: 740.4148). Theoretical element content (%) C 56 H 40 D 7 N: c,90.77; h,7.34; n,1.89. Measured element content (%): c,90.80; h,7.31; n,1.92.
Synthesis example 23: preparation of Compound 293
The same preparation method as in Synthesis example 4 was followed except that a-10 was replaced with equimolar a-221, b-10 was replaced with equimolar b-293, and c-10 was replaced with equimolar c-48, to obtain compound 293 (19.52 g), and the purity of the solid was ≡ 99.92% by HPLC detection. Mass spectrum m/z:677.3094 (theory: 677.3083). Theoretical element content (%) C 52 H 39 N: c,92.13; h,5.80; n,2.07. Measured element content (%): c,92.09; h,5.77; n,2.10.
Synthesis example 24: preparation of Compound 424
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-221, b-10 was replaced with equimolar b-424, and c-10 was replaced with equimolar c-128 to obtain compound 424 (22.09 g), and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:951.4792 (theory: 951.4804). Theoretical element content (%) C 73 H 61 N: c,92.07; h,6.46; n,1.47. Measured element content (%): c,92.10; h,6.44; n,1.50.
Synthesis example 25: preparation of Compound 427
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-427, and c-10 was replaced with equimolar c-427, to obtain Compound 427 (20.74 g), and the purity of the solid was ≡ 99.91% by HPLC. Mass spectrum m/z:835.3937 (theory: 835.3926). Theoretical element content (%) C 62 H 49 N 3 : c,89.07; h,5.91; n,5.03. Measured element content (%): c,89.10; h,5.88; n,5.05.
Synthesis example 26: preparation of Compound 434
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar n-427, b-10 was replaced with equimolar b-434, and c-10 was replaced with equimolar c-128 to obtain compound 434 (19.10 g), and the purity of the solid was ≡ 99.95% by HPLC detection. Mass spectrum m/z:691.2888 (theory: 691.2875). Theoretical element content (%) C 52 H 37 NO: c,90.27; h,5.39; n,2.02. Measured element content (%): c,90.32; h,5.43; n,2.03.
Synthesis example 27: preparation of Compound 482
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-221, b-10 was replaced with equimolar b-482 and c-10 was replaced with equimolar c-482 to obtain compound 482 (19.96 g) having a solid purity of ≡ 99.97% by HPLC. Mass spectrum m/z:787.3229 (theory: 787.3211). Theoretical element content (%) C 58 H 37 D 4 NS: c,88.40; h,5.75; n,1.78. Measured element content (%): c,88.37; h,5.78; n,1.82.
Synthesis example 28: preparation of Compound 499
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-499, and c-10 was replaced with equimolar c-499, to obtain compound 499 (19.99 g), and the purity of the solid was. Mass spectrum m/z:846.3923 (theory: 846.3912). Theoretical element content (%) C 64 H 42 D 4 N 2 : c,90.74; h,5.95; n,3.31. Measured element content (%): c,90.69; h,5.98; n,3.27.
Synthesis example 29: preparation of Compound 525
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-525 and c-10 was replaced with equimolar c-525 to obtain compound 525 (19.95 g), and the purity of the solid was ≡ 99.96% by HPLC. Mass spectrum m/z:713.2151 (theory: 713.2138). Theoretical element content (%) C 49 H 37 GeN: c,82.61; h,5.23; n,1.97. Measured element content (%): c,82.56; h,5.19; n,1.93.
Synthesis example 40: preparation of Compound 560
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-560, b-10 was replaced with equimolar b-293, and c-10 was replaced with equimolar c-525 to obtain compound 560 (20.66 g), and the purity of the solid was ≡ 99.92% by HPLC. Mass spectrum m/z:753.2441 (theory: 753.2451). Theoretical element content (%) C 52 H 41 GeN: c,83.00; h,5.49; n,1.86. Measured element content (%): c,83.03; h,5.45; n,1.88.
Synthesis example 41: preparation of Compound 577
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-577, b-10 was replaced with equimolar b-577, and c-10 was replaced with equimolar c-525 to obtain compound 577 (20.65 g), and the purity of the solid was not less than 99.94% as measured by HPLC. Mass spectrum m/z:820.2907 (theory: 820.2921). Theoretical element content (%) C 57 H 38 D 5 GeN: c,83.53; h,5.90; n,1.71. Measured element content (%): c,83.48; h,5.86; n,1.75.
Synthesis example 42: preparation of Compound 602
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-602, b-10 was replaced with equimolar b-75, and c-10 was replaced with equimolar c-602 to obtain compound 602 (21.17 g), and the purity of the solid was ≡ 99.91% by HPLC detection. Mass spectrum m/z:913.2752 (theory: 913.2764). Theoretical element content (%) C 65 H 45 GeN: c,85.54; h,4.97; n,1.53. Measured element content (%): c,85.49; h,5.01; n,1.50.
Synthesis example 43: preparation of Compound 627
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-627, and c-10 was replaced with equimolar c-627, to obtain compound 627 (21.61 g), and the purity of the solid was ≡ 99.94% by HPLC detection. Mass spectrum m/z:916.2860 (theory: 916.2873). Theoretical element content (%) C 64 H 46 GeN 2 : c,83.95; h,5.06; n,3.06. Measured element content (%): c,83.98; h,5.10; n,3.03.
Synthesis example 44: preparation of Compound 632
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar a-632, b-10 was replaced with equimolar b-632, and c-10 was replaced with equimolar c-525 to obtain Compound 632 (21.88 g), and the purity of the solid was ≡ 99.92% by HPLC detection. Mass spectrum m/z:855.2908 (theory: 855.2920). Theoretical element content (%) C 60 H 47 GeN: c,84.32; h,5.54; n,1.64. Measured element content (%): c,84.27; h,5.56; n,1.69.
Synthesis example 45: preparation of Compound 644
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-644, and c-10 was replaced with equimolar c-644 to give compound 644 (22.59 g), and the purity of the solid was ≡ 99.95% by HPLC. Mass spectrum m/z:1027.3221 (theory: 1027.3233). Theoretical element content (%) C 74 H 51 GeN: c,86.56; h,5.01; n,1.36. Measured element content (%): c,86.61; h,4.98; n,1.40.
Synthesis example 46: preparation of Compound 648
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-648, and c-10 was replaced with equimolar c-525 to give compound 648 (21.97 g), and the purity of the solid was ≡ 99.93% by HPLC detection. Mass spectrum m/z:931.3245 (theory: 931.3233). Theoretical element content (%) C 66 H 51 GeN: c,85.17; h,5.52; n,1.50. Measured element content (%): c,85.22; h,5.49; n,1.54.
Synthesis example 47: preparation of Compound 652
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-48, b-10 was replaced with equimolar b-652, and c-10 was replaced with equimolar c-525 to obtain Compound 652 (21.98 g), and the purity of the solid was ≡ 99.95% by HPLC detection. Mass spectrum m/z:901.2751 (theory: 901.2764). Theoretical element content (%) C 64 H 45 GeN: c,85.35; h,5.04; n,1.56. Measured element content (%): c,85.40; h,5.01; n,1.60.
Synthesis example 48: preparation of Compound 685
The same preparation as in Synthesis example 4 was repeated except that a-10 was replaced with equimolar c-128, b-10 was replaced with equimolar b-685, and c-10 was replaced with equimolar c-525, to obtain Compound 685 (20.36 g), and the purity of the solid was. Mass spectrum m/z:760.2539 (theory: 760.2526). Theoretical element content (%) C 51 H 30 D 7 GeNO: c,80.65; h,5.84; n,1.84. Actual measurement elementContent (%): c,80.70; h,5.87; n,1.80.
Device embodiment
In the invention, an ITO glass substrate is ultrasonically cleaned by 5% glass cleaning liquid for 2 times each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times each for 10 minutes. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. The organic materials are sublimated, and the purity is over 99.99 percent.
Test software, a computer, a K2400 digital source list manufactured by Keithley company in U.S. and a PR788 spectrum scanning luminance meter manufactured by Photo Research company in U.S. are combined into a combined IVL test system to test the driving voltage, luminous efficiency and CIE color coordinates of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature.
The preparation of the device is completed by adopting a vacuum evaporation system and continuously evaporating under the condition of continuous vacuum. The materials are respectively arranged in quartz crucibles of different evaporation sources, and the temperature of the evaporation sources can be controlled independently. The thermal evaporation rate of the organic material is generally set at 0.1nm/s, and the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5×10 during the film manufacturing process -5 Under Pa, the organic layer and the metal electrode were vapor deposited by replacing the mask plate, the vapor deposition rate was detected by using an Infinion SQM160 quartz crystal film thickness detector, and the film thickness was detected by using a quartz crystal oscillator.
Red organic electroluminescent device
Example 1: preparation of organic electroluminescent device 1
ITO is used as an anode on the glass substrate; forming a hole injection layer by vacuum evaporation of 55nm F4-TCNQ on the anode; forming a first hole transport layer by vacuum evaporation of 30nm of the compound 10 of the present invention on the hole injection layer; vacuum vapor deposition of 30nm MCP: ir (BT) on the first hole-transporting layer 2 (acac) (mass ratio 95%:5% mixed) to form a light emitting layer; vacuum evaporation of 28nm Alq on light-emitting layer 3 Forming an electron transport layer; on the electron-transport layer Vacuum evaporating Liq of 1.0nm to form an electron injection layer; al of 120nm was vacuum-evaporated on the electron injection layer to form a cathode.
Examples 2 to 35: preparation of organic electroluminescent devices 2 to 35
The organic electroluminescent devices 2 to 35 were obtained by replacing the first hole transport layer in example 1 with the first hole transport layer in the form of compound 27, 34, 48, 60, 75, 89, 96, 98, 104, 107, 128, 146, 169, 180, 187, 202, 221, 268, 293, 409, 424, 427, 434, 482, 525, 560, 577, 602, 627, 632, 644, 648, 652, 685, and the other steps were the same.
Comparative examples 1 to 3: preparation of comparative organic electroluminescent devices 1 to 3
The compound 10 in the first hole transport layer of example 1 was changed to R-1, R-2, R-3, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 3.
The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 1 to 35 of the present invention and comparative examples 1 to 3 are shown in table 1.
Table 1 light emission characteristic test data of organic electroluminescent device
Note that: t95 means that the current density is 10mA/cm 2 In the case, the time taken for the brightness of the device to decay to 95%;
as can be seen from table 1, when the triarylamine derivative of formula 1 of the present invention is used for the first hole transport layer in an organic electroluminescent device, the luminous efficiency and the service life of the organic electroluminescent device are improved as compared with comparative examples 1 to 3.
Green organic electroluminescent device
Example 36: preparation of organic electroluminescent device 36
ITO is used as an anode on the glass substrate; vacuum evaporating 58nm HAT-CN on the anode to form a hole injection layer; vacuum evaporating NPB of 30nm on the hole injection layer to form a first hole transport layer; vacuum evaporating the compound 10 of the invention as a second hole transport layer on the first hole transport layer to a thickness of 15nm; vacuum evaporating 35nm BCzPh to TmCzTrz (mass ratio of 95% to 5% mixture) on the second hole transport layer to form a luminescent layer; vacuum evaporating Liq of 25nm on the light-emitting layer to form an electron transport layer; vacuum evaporating LiF of 1.0nm on the electron transport layer to form an electron injection layer; al of 120nm was vacuum-evaporated on the electron injection layer to form a cathode.
Examples 37 to 70: preparation of organic electroluminescent devices 37-70
The organic electroluminescent devices 37 to 70 were obtained by replacing the compound 10 in the second hole-transporting layer of example 36 with the compound 27, the compound 34, the compound 48, the compound 60, the compound 75, the compound 89, the compound 96, the compound 98, the compound 104, the compound 107, the compound 128, the compound 146, the compound 169, the compound 180, the compound 187, the compound 202, the compound 221, the compound 268, the compound 293, the compound 409, the compound 424, the compound 427, the compound 434, the compound 482, the compound 525, the compound 560, the compound 577, the compound 602, the compound 627, the compound 632, the compound 644, the compound 648, the compound 652, the compound 685, respectively, and the other steps being the same.
Example 71: preparation of organic electroluminescent device 71
The organic electroluminescent device 71 was obtained by replacing the compound NPB in the first hole transport layer of example 36 with the compound 75, and replacing the compound 10 in the second hole transport layer with the compound 75 in the same manner.
Example 72: preparation of organic electroluminescent device 72
The organic electroluminescent device 72 was obtained by replacing compound NPB in the first hole transport layer of example 36 with compound 96, and replacing compound 10 in the second hole transport layer with compound 180, in the same manner.
Example 73: preparation of organic electroluminescent device 73
The organic electroluminescent device 73 was obtained by replacing the compound NPB in the first hole transport layer of example 36 with the compound 293, and replacing the compound 10 in the second hole transport layer with the compound 146 in the same manner.
Example 74: preparation of organic electroluminescent device 74
The organic electroluminescent device 74 was obtained by replacing the compound NPB in the first hole transport layer of example 36 with the compound 10, and replacing the compound 10 in the second hole transport layer with the compound 75, in the same manner.
Example 75: preparation of organic electroluminescent device 75
The organic electroluminescent device 75 was obtained by replacing the compound NPB in the first hole transport layer of example 36 with the compound 89, and replacing the compound 10 in the second hole transport layer with the compound 644, in the same manner.
Comparative examples 4 to 5: preparation of comparative organic electroluminescent devices 4 to 5
The compound 10 in the second hole transport layer of example 36 was changed to R-4 and R-5, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 4 to 5.
The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 36 to 75 of the present invention and comparative examples 4 to 5 are shown in table 2.
Table 2 light emission characteristic test data of organic electroluminescent device
Note that: t95 means that the current density is 10mA/cm 2 In the case, the time taken for the brightness of the device to decay to 95%;
as can be seen from the results of table 2, when the triarylamine derivative of the present invention is applied to an organic electroluminescent device as a second hole transport layer material, the device performance is significantly improved compared with comparative examples 4 to 5, and the advantages of high luminous efficiency and long service life are exhibited. When the triarylamine derivative of the present invention is used in an organic electroluminescent device as a first hole transport layer material and a second hole transport layer material, both the luminous efficiency and the service life are improved as compared with comparative examples 4 to 5. This is because the triarylamine structure in the compound of the present invention has a group containing C, si, ge elements connected through the 1,4 positions, improving the carrier transport efficiency, and therefore, when the triarylamine derivative of the present invention is used as a hole transport material for an organic electroluminescent device, the organic electroluminescent device exhibits higher luminous efficiency and longer service life.
It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.

Claims (10)

1. A triarylamine derivative is characterized by having a structural general formula shown in a formula 1,
wherein the Ar is 1 Selected from the group represented by formula a or formula b,
the X is selected from C, si and Ge, and the Ra and the R are b Independently selected from a substituted or unsubstituted C1 to C15 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group; the R is 3 、R 4 Independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 aliphatic ring, and fused ring group of C6-C30 aromatic ring; said n 3 Selected from 0, 1, 2 or 3; said n 4 Selected from 0, 1, 2, 3 or 4;
the Ar is as follows 2 A substituted or unsubstituted C6 to C30 aryl or a substituted or unsubstituted C2 to C30 heteroaryl;
the Ar is as follows 3 Selected from the group consisting of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;
The R is 1 、R 2 Independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C60 aliphatic ring and fused ring group of C6-C30 aromatic ring, or optionally adjacent two R 1 Bonded together to form a substituted or unsubstituted cyclic structure, or optionally two adjacent R' s 2 Bonded together to form a substituted or unsubstituted cyclic structure; said n 1 Selected from 0, 1, 2, 3Or 4; said n 2 Selected from 0, 1, 2, 3 or 4;
the L is 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group.
2. The triarylamine derivative of claim 1 wherein Ar 1 One selected from the group consisting of:
the Ra, R is b Independently selected from the group consisting of substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl-substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinoxalinyl, and substituted or unsubstituted quinazolinyl;
The R is 3 、R 4 Independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted nonyl, substituted or unsubstituted decyl, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted phenyldimethylsilyl, substituted or unsubstituted diphenylmethylsilyl, substituted or unsubstituted dimethylethylsilyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstitutedA cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted camphene group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted benzocyclopropane group, a substituted or unsubstituted benzocyclobutane group, a substituted or unsubstituted benzocyclopentane group, a substituted or unsubstituted benzocyclohexenyl group, a substituted or unsubstituted benzocycloheptane group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dihydronaphthyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group; in the case of being substituted with a plurality of substituents, the plurality of substituents are the same or different from each other;
Said n 3 Selected from 0, 1, 2 or 3; said n 4 Selected from 0, 1, 2, 3 or 4.
3. The triarylamine derivative of claim 1 wherein Ar 1 One selected from the group consisting of:
the R is 3 、R 4 Independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted triethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted camphenethyl, substituted or unsubstituted norbornyl, substituted or unsubstituted benzocyclopropenyl, substituted or unsubstituted benzocyclobutanyl, substituted or unsubstituted benzocycloheptyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, unsubstituted pyridinyl, unsubstituted or unsubstituted pyridinyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other;
The R is 5 The same or different is selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl,A substituted or unsubstituted octyl group, a substituted or unsubstituted trimethylsilyl group, a substituted or unsubstituted triethylsilyl group, a substituted or unsubstituted triphenylsilyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted campanyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted benzocyclopropanyl group, a substituted or unsubstituted benzocyclobutanyl group, a substituted or unsubstituted benzocyclopentanyl group, a substituted or unsubstituted benzocyclohexenyl group, a substituted or unsubstituted benzocycloheptane group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and in the case of being substituted with a plurality of substituents, the plurality of substituents are the same as or different from each other;
Said n 3 Selected from 0, 1, 2 or 3; said n 4 Selected from 0, 1, 2, 3 or 4; said n 5 Selected from 0, 1, 2, 3, 4 or 5; said n 6 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; said n 7 Selected from 0, 1, 2, 3, 4, 5 or 6.
4. The triarylamine derivative of claim 1 wherein Ar 2 One selected from the group consisting of:
wherein the R is f One selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 aliphatic ring and C6-C30 aromatic ring fused ring group;
said f 1 Selected from 0, 1, 2, 3, 4 or 5;
said f 2 Selected from 0, 1, 2, 3 or 4;
said f 3 Selected from 0, 1, 2 or 3;
said f 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7;
said f 5 Selected from 0, 1, 2, 3, 4, 5 or 6;
said f 6 Selected from 0, 1 or 2;
the "×" indicates the binding site to an adjacent atom.
5. The triarylamine derivative of claim 1 wherein Ar 3 One selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinoxalinyl group, and a substituted or unsubstituted quinazolinyl group.
6. The triarylamine derivative of claim 1 wherein Ar 3 One selected from the group consisting of:
wherein the R is g One or more selected from deuterium, cyano, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, in the case of being substituted with a plurality of substituents, the plurality of substituents being the same as or different from each other;
Said g 1 Selected from 0, 1, 2, 3, 4 or 5;
said g 2 Selected from 0, 1, 2, 3 or 4;
said g 3 Selected from 0, 1, 2 or 3;
said g 4 Selected from 0, 1, 2, 3, 4, 5, 6 or 7;
said g 5 Selected from 0, 1, 2, 3, 4, 5 or 6.
7. The triarylamine derivative of claim 1 wherein L 1 、L 2 、L 3 Independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted pyridylene group, or a substituted or unsubstituted pyrimidinylene group.
8. The triarylamine derivative of claim 1 wherein the triarylamine derivative of formula 1 is selected from one of the structures shown below:
9. an organic electroluminescent device comprising an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more of the anode and the cathode, wherein the organic layer contains any one of the triarylamine derivatives according to any one of claims 1 to 8.
10. An organic electroluminescent device according to claim 9, wherein the organic layer comprises a hole transport region, a light emitting layer, an electron transport region or a capping layer, wherein at least one layer of the hole transport region comprises any one of the triarylamine derivatives of claims 1 to 8.
CN202311068896.2A 2023-08-23 2023-08-23 Triarylamine derivative and organic electroluminescent device thereof Pending CN117126190A (en)

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