阅读说明：本技术 一种三芳胺化合物及其有机发光器件 (Triarylamine compound and organic light-emitting device thereof ) 是由 韩春雪 陆影 董秀芹 孙敬 于 2021-09-09 设计创作，主要内容包括：本发明提供一种三芳胺化合物及其有机发光器件,涉及有机光电材料技术领域。本发明化合物以三芳胺为中心,引入在芴基的9位上连接二苯并五元环或二苯并六元环基团,并再引入在芴的9位上连接金刚烷基或降冰片烷基作为大体积烷烃基团,两种特定基团的引入,使得该类材料具有适宜的空穴迁移率,从而提高有机发光器件的发光效率、使用寿命以及降低器件的驱动电压。并且本发明提供的三芳胺化合物作为覆盖层材料应用于有机发光器件中,能够提高有机发光器件的发光效率,同时也能够延长器件的寿命。本发明的三芳胺化合物具有良好的物理和热学稳定性,可广泛应用于面板显示、照明光源、有机太阳能电池、有机感光体或有机薄膜晶体管等领域。(The invention provides a triarylamine compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The compound takes triarylamine as a center, introduces dibenzo five-membered ring or dibenzo six-membered ring group connected to 9 site of fluorene, introduces adamantyl or norbornyl connected to 9 site of fluorene as a large-volume alkane group, and introduces two specific groups, so that the material has proper hole mobility, thereby improving the luminous efficiency and the service life of the organic light-emitting device and reducing the driving voltage of the device. The triarylamine compound provided by the invention is used as a covering layer material to be applied to an organic light-emitting device, so that the luminous efficiency of the organic light-emitting device can be improved, and the service life of the device can be prolonged. The triarylamine compound has good physical and thermal stability, and can be widely applied to the fields of panel display, lighting sources, organic solar cells, organic photoreceptors or organic thin film transistors and the like.)

1. A triarylamine compound is characterized in that the molecular structure is shown as formula I:

wherein, the ring A is selected from one of the groups shown in formula a, formula b and formula c:

the R is_m、R_nIndependently selected from any one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C15 and aryl of C6-C25; m is selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 or 10; n is selected from 0, 1,2, 3, 4, 5, 6, 7 or 8; "" is a connection site;

said X₀Selected from O, S, CR_aR_b、NR_cWherein said R is_aAnd R_bEach independently is one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl, or are combined with each other to formA condensed ring represented by wherein R_dAny one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C12, aryl of C6-C25 and heteroaryl of C2-C25 which are the same or different is used for forming a binding site; r_cOne selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

the E is selected from a single bond, O, S or CR ' R ', R ' is same or different from each other and is selected from one of methyl, ethyl, isopropyl, tertiary butyl and phenyl;

ar is selected from one of deuterium, halogen atoms, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

the R is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

said L₀、L₁、L₂、L_mIndependently selected from a single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C2-C20;

the R is₀、R₁、R₂、R₃、R₄The same or different from each other, and each is independently selected from one of hydrogen, deuterium, halogen atom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, or adjacent R₀Adjacent R₁Adjacent R₂Adjacent R₃Adjacent R₄Can be connected into a ring structure;

a is selected from 0, 1,2, 3 or 4;

b is selected from 0, 1,2, 3 or 4;

c is selected from 0, 1,2 or 3;

d is selected from 0, 1,2, 3 or 4;

n is₁Selected from 0, 1,2 or 3;

in the above "substituted or unsubstituted …", the term "substituted …" means that the substituted aryl group is substituted with at least one substituent independently selected from the group consisting of deuterium, a cyano group, an alkyl group having from C1 to C15, a cycloalkyl group having from C3 to C15, an aryl group having from C6 to C25, and a heteroaryl group having from C2 to C20.

2. A triarylamine compound according to claim 1, wherein Ar is selected from any one of the following groups:

the R is₁₂One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

the R is₁₃One selected from deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or adjacent R₁₃Can be connected into a ring structure;

wherein said R₁₃Can also be substituted by R₂₃Substituted, R₂₃One or more substituents selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, and dibenzofuranyl, and in the case of substitution with a plurality of substituents, the plurality of substituents may be the same as or different from each other;

at least one X is selected from N and the remaining X are selected from CR₁₃；

A' is 0, 1 or 2; a is a₀Is 0, 1,2 or 3; a is a₁Is 0, 1,2, 3 or 4; a is a₂Is 0, 1,2, 3, 4 or 5; a is a₃Is 0, 1,2, 3, 4, 5, 6 or 7; a is a₄Is 0, 1,2, 3, 4, 5, 6, 7 or 8; a is a₅Is 0, 1,2, 3, 4, 5, 6, 7, 8 or 9.

3. A triarylamine compound according to claim 1 wherein R in said ring A is_m、R_nIndependently selected from one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated n-butyl, deuterated isopropyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclobutyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated cycloheptyl, phenyl and pentadeuterated phenyl.

4. A triarylamine compound according to claim 1 wherein said formula a is selected from one of the following groups:

the formula b is selected from one of the following groups:

the formula c is selected from one of the following groups:

5. a triarylamine compound according to claim 1 wherein R is a tertiary amine compound₀、R₁、R₂、R₃、R₄Are identical or different from one another and are each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, cyano, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, phenyl-naphthyl, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazolyl9-phenylcarbazolyl, pyrenyl, indolyl, acridinyl, pyridyl, furyl, thienyl, benzothienyl, benzofuryl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzothienyl, dibenzofuryl, phenothiazinyl, phenoxazinyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, deuterated terphenyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylenyl, deuterated phenyl-naphthyl, deuterated phenyl-deuterated naphthyl, dibenzothienyl, deuterated dibenzofuryl, deuterated 9, 9-dimethylfluorenyl, deuterated 9, 9-diphenylfluorenyl, deuterated spirobifluorenyl, or adjacent R₀Adjacent R₁Adjacent R₂Adjacent R₃Adjacent R₄Can be connected into a ring structure.

6. A triarylamine compound according to claim 1 wherein L is an aryl amine₀、L₁、L₂、L_mIndependently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted 9, 9-diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted triphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9-phenylcarbazolyl, substituted or unsubstituted benzoxadiazolyl, substituted or unsubstituted benzothiadiazolyl, substituted or unsubstituted phenylene-naphthylene, wherein the substituent is deuterium, methyl, ethyl, isopropyl, or a mixture thereof, One or more of tert-butyl, phenyl and pentadeuterophenyl, wherein when substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other.

7. A triarylamine compound according to claim 1 wherein said triarylamine compound is selected from any one of the following chemical structures:

8. an organic light-emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode or outside one or more electrodes selected from the anode and the cathode, wherein the organic layer contains any one or a combination of at least two of the triarylamine compounds described in any one of claims 1 to 7.

9. An organic light-emitting device according to claim 8, wherein the organic layer comprises a hole transport layer containing any one or a combination of at least two of the triarylamine compounds defined in any one of claims 1 to 7.

10. An organic light-emitting device according to claim 8, wherein the organic layer comprises a capping layer containing any one or a combination of at least two of the triarylamine compounds defined in any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a triarylamine compound and an organic light-emitting device thereof.

Background

In the organic light emitting device, a voltage is applied between an anode and a cathode, holes are injected from the anode, electrons are injected from the cathode, the holes and the electrons pass through the respective organic functional layers, and then combine with each other in a light emitting layer to form excitons, and light is generated in the process of changing the excitons from an excited state to a ground state. The organic light emitting device has the advantages of active light emission, high response speed, wide viewing angle, low driving voltage, ultra-thin portability, low cost, flexibility, capability of manufacturing large-size and curved panels and the like, and compared with an inorganic light emitting diode, the organic light emitting device also has the advantage of easily modulating colors to realize full-color display, and the organic light emitting device is increasingly applied to the display market and becomes the most potential panel display technology at present.

In the organic light emitting device, the organic layers can be roughly classified into the following categories according to the function of materials: hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer, capping layer, and the like. The hole injection layer, the hole transport layer, the electron injection layer and other carrier injection transport layers are mainly used for reducing injection barriers of holes and electrons, so that the injection rate and the recombination rate of carriers in the light emitting layer are improved, the light emitting efficiency of the device is improved, and the service life of the device is prolonged; the luminescent layer generally adopts a mode of doping a luminescent layer host and a guest, the luminescent layer guest doping material is used as a luminescent material, the luminescent layer host is generally used for realizing energy transfer and preventing the concentration quenching of excitons so as to realize the effective utilization of luminescence; the covering layer is generally positioned on the outer layer of the cathode of the device and is commonly arranged on a top emission device, and is used for reducing the negative influence caused by the waveguide effect and the plasma element effect, effectively improving the light output efficiency of the device, further improving the luminous efficiency of the device, leading out energy in time and avoiding heat accumulation deterioration in the device, thereby greatly prolonging the service life of the device.

With the social demands and the requirements of industrial production, the development direction of future organic light emitting devices is white light devices and full-color display devices with high efficiency, high brightness, long service life and low cost, and the improvement of materials is a crucial link, wherein the improvement of injection and transmission materials mainly relates to the adjustment of energy gaps, and is used for reducing injection potential barriers and driving voltages of the devices, adjusting carrier injection balance, improving the film forming property and film stability of the materials, further improving the light emitting efficiency of the devices and prolonging the service life. The improvement of the covering layer mainly relates to the improvement of the refractive index, the reduction of the absorption coefficient of a visible light wave band, the improvement of the stability, the durability and the anti-UV damage performance of the film and the like. Therefore, the development of an organic light-emitting material which can reduce the driving voltage of the device, reduce the energy consumption, improve the light-emitting efficiency of the device and prolong the service life of the device becomes a problem to be solved urgently.

Disclosure of Invention

The present invention aims to provide a triarylamine compound and an organic light emitting device thereof, based on the prior art and aiming at industrialization, the organic light emitting device prepared by using the triarylamine compound is applied to a hole transport layer or an auxiliary hole transport layer (a second hole transport layer) to develop an organic light emitting device with low driving voltage, high luminous efficiency and long service life, or is applied to a cover layer to improve the luminous efficiency and the service life of the organic light emitting device, and the molecular structure formula is shown as formula i:

wherein, the ring A is selected from one of the groups shown in formula a, formula b and formula c:

the R is_m、R_nIndependently selected from any one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C15 and aryl of C6-C25; m is selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 or 10; n is selected from 0, 1,2, 3, 4, 5, 6, 7 or 8; "" is a connection site;

said X₀Selected from O, S, CR_aR_b、NR_cWherein said R is_aAnd R_bEach independently is one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl, or are combined with each other to formA condensed ring represented by wherein R_dAny one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C12, aryl of C6-C25 and heteroaryl of C2-C25 which are the same or different is used for forming a binding site; r_cOne selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

the E is selected from a single bond, O, S or CR ' R ', R ' is same or different from each other and is selected from one of methyl, ethyl, isopropyl, tertiary butyl and phenyl;

ar is selected from one of deuterium, halogen atoms, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

the R is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

said L₀、L₁、L₂、L_mIndependently selected from a single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C2-C20;

the R is₀、R₁、R₂、R₃、R₄The same or different from each other, and each is independently selected from one of hydrogen, deuterium, halogen atom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, or adjacent R₀Adjacent R₁Adjacent R₂Adjacent R₃Adjacent R₄Can be connected into a ring structure;

a is selected from 0, 1,2, 3 or 4;

b is selected from 0, 1,2, 3 or 4;

c is selected from 0, 1,2 or 3;

d is selected from 0, 1,2, 3 or 4;

n is₁Selected from 0, 1,2 or 3.

The invention also provides an organic light-emitting device which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or positioned outside more than one of the anode and the cathode, and the organic layer contains any one or the combination of at least two of the triarylamine compounds.

The invention has the beneficial effects that:

the invention provides a triarylamine compound and an organic light-emitting device thereof, wherein the compound takes triarylamine as a center, a dibenzo five-membered ring or a dibenzo six-membered ring is connected to a 9-position of a fluorenyl group as a substituent group on the triarylamine, the introduction of the substituent group can reduce the conjugation degree of the compound so as to reduce the hole mobility, and the introduction of another substituent group is that an adamantyl group or a norbornane group is connected to the 9-position of fluorene as a bulky alkane group, compared with an aromatic group, the electron density of the fluorene ring and the whole conjugation system is improved through a super-conjugation effect, the hole mobility of the material can be enhanced, and the introduction of two specific groups enables the material to have proper hole mobility so as to improve the light-emitting efficiency of the organic light-emitting device and the service life of the device; and an alkane group with large volume steric hindrance is introduced, so that the HOMO energy level can be easily regulated, the HOMO value of a material more suitable for an adjacent layer is obtained, and the driving voltage of the device is reduced.

The triarylamine compound is used as a covering layer material to be applied to an organic light-emitting device, can effectively solve the problem of total emission of an interface between an ITO film and a glass substrate and an interface between the glass substrate and air, reduces total reflection loss and waveguide loss in the OLED device, and improves light extraction efficiency, thereby improving the light-emitting efficiency of the organic light-emitting device. In addition, the triarylamine compound can improve the molecular weight of the material, reduce the molecular symmetry, improve the glass transition temperature and the evaporation temperature of the material, control the crystallinity of the material, have good physical and thermal stability and prolong the service life of an organic light-emitting device on the premise of avoiding an over-strong pi-pi stacking effect.

Detailed Description

The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.

Halogen as referred to herein means fluorine, chlorine, bromine and iodine.

The alkyl group in the present invention refers to a hydrocarbon group obtained by dropping one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group or a branched-chain alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but is not limited thereto; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, the isomeric form of n-pentyl, the isomeric form of n-hexyl, the isomeric form of n-heptyl, the isomeric form of n-octyl, the isomeric form of n-nonyl, the isomeric form of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The cycloalkyl group in the present invention refers to a hydrocarbon group obtained by removing one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms, and examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, bornyl, norbornyl, and the like. The cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group or a norbornyl group.

The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic compound molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the fused ring aryl group refers to an aryl group in which two or more aromatic rings are contained in a molecule and are fused together by sharing two adjacent carbon atoms, and examples thereof include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, and the like. The above aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylene group, or a spirobifluorenyl group.

The heteroaryl group in the present invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group with a heteroatom, including but not limited to oxygen, sulfur, nitrogen or phosphorus atom, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes pyridyl, pyrimidyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group or a phenoxathiyl group.

The alkenyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from an olefin molecule, and includes a monoalkenyl group, a dienyl group, a polyalkenyl group, and the like. Preferably from 2 to 60 carbon atoms, more preferably from 2 to 30 carbon atoms, particularly preferably from 2 to 15 carbon atoms, most preferably from 2 to 6 carbon atoms. Examples of the alkenyl group include vinyl, butadienyl and the like, but are not limited thereto. The alkenyl group is preferably a vinyl group.

The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from the aromatic core carbon of the aromatic compound molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring arylene group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene group includes phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenylene, and the like; the condensed ring arylene group includes naphthylene, anthrylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, fluoranthenylene, phenylfluorenylene, and the like, but is not limited thereto. The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a fluorenylene group, or a phenylfluorenylene group.

Heteroarylene as used herein refers to the generic term for groups in which one or more of the aromatic core carbons in the arylene group is replaced with a heteroatom, including, but not limited to, oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the linking site of the heteroarylene group may be located on a ring-forming carbon atom or on a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes a pyridylene group, a pyrimidylene group, a triazinylene group, a furanylene group, a thiophenylene group and the like, but is not limited thereto; the polycyclic heteroarylene group includes bipyridyl idene, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroarylene group includes, but is not limited to, a quinolylene group, an isoquinolylene group, an indolyl group, a benzothiophene group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolylene group, a benzothiazolyl group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group, an acridinylene group, a9, 10-dihydroacridine group, a phenoxazinyl group, a phenothiazinylene group, a phenoxathiin group and the like. The heteroaryl group is preferably a pyridylene group, pyrimidylene group, thienylene group, furylene group, benzothienylene group, benzofuranylene group, benzoxazolyl group, benzimidazolylene group, benzothiazolyl group, dibenzofuranylene group, dibenzothiophenylene group, dibenzofuranylene group, carbazolyl group, acridinylene group, phenoxazinyl group, phenothiazinylene group, phenoxathiin group.

The term "substituted …" as used herein, such as substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, etc., means mono-or poly-substituted with groups independently selected from, but not limited to, deuteroyl, halogen, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, substituted or unsubstituted amine, etc., preferably with groups selected from, but not limited to, deuteroyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, tolyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9-diphenylfluorenyl, 9-diphenylfluorenyl, and the like, Groups of dianilino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuryl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuryl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl are mono-or polysubstituted. In addition, the above substituents may be substituted with one or more substituents selected from deuterium, a halogen atom, cyano, alkyl, cycloalkyl, and aryl.

The term "ring" as used herein, unless otherwise specified, refers to a fused ring consisting of an aromatic ring having 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms, or a heterocyclic ring having 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, or a combination thereof, which contains a saturated or unsaturated ring.

In this specification, when a substituent is not fixed in position on a ring, it means that it can be attached to any of the respective optional sites of the ring. For example,can representAnd so on.

The bonding to form a cyclic structure according to the present invention means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:

in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclopentane, cyclohexane acene, pyridine, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but not limited thereto.

The invention provides a triarylamine compound, the molecular structural general formula of which is shown as formula I:

wherein, the ring A is selected from one of the groups shown in formula a, formula b and formula c:

the R is_m、R_nIndependently selected from any one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C15 and aryl of C6-C25; m is selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 or 10; n is selected from 0, 1,2, 3, 4, 5, 6, 7 or 8; "" is a connection site;

said X₀Selected from O, S, CR_aR_b、NR_cWherein said R is_aAnd R_bEach independently is one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl, or are combined with each other to formA condensed ring represented by wherein R_dAny one of hydrogen, deuterium, alkyl of C1-C6, cycloalkyl of C3-C12, aryl of C6-C25 and heteroaryl of C2-C25 which are the same or different is used for forming a binding site; r_cOne selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

the E is selected from a single bond, O, S or CR ' R ', R ' is same or different from each other and is selected from one of methyl, ethyl, isopropyl, tertiary butyl and phenyl;

ar is selected from one of deuterium, halogen atoms, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

the R is selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C25 heteroaryl;

said L₀、L₁、L₂、L_mIndependently selected from a single bond, substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C2-C20;

the R is₀、R₁、R₂、R₃、R₄The same or different from each other, and each is independently selected from one of hydrogen, deuterium, halogen atom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, or adjacent R₀Adjacent R₁Adjacent R₂Adjacent R₃Adjacent R₄Can be connected into a ring structure;

a is selected from 0, 1,2, 3 or 4;

b is selected from 0, 1,2, 3 or 4;

c is selected from 0, 1,2 or 3;

d is selected from 0, 1,2, 3 or 4;

n is₁Selected from 0, 1,2 or 3.

Preferably, "substituted …" in "substituted or unsubstituted …" means being substituted with one or more substituents independently selected from the group consisting of deuterium, cyano, alkyl group of C1 to C15, cycloalkyl group of C3 to C15, aryl group of C6 to C25, and heteroaryl group of C2 to C20.

Preferably, Ar is selected from one of the following groups:

the R is₁₂One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

the R is₁₃One selected from deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or adjacent R₁₃Can be connected into a ring structure;

wherein said R₁₃Can also be substituted by R₂₃Substituted, R₂₃One or more substituents selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, and dibenzofuranyl, and in the case of substitution with a plurality of substituents, the plurality of substituents may be the same as or different from each other;

at least one X is selected from N, and the rest X is selected from CR₁₃；

A' is 0, 1 or 2; a is a₀Is 0, 1,2 or 3; a is a₁Is 0, 1,2, 3 or 4; a is a₂Is 0, 1,2, 3, 4 or 5; a is a₃Is 0, 1,2, 3, 4, 5, 6 or 7; a is a₄Is 0, 1,2, 3, 4, 5, 6, 7 or 8; a is a₅Is 0, 1,2,4, 5, 6, 7, 8 or 9.

Preferably, Ar is selected from one of the following groups:

preferably, R in the ring A_m、R_nIndependently selected from one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated n-butyl, deuterated isopropyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclobutyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated cycloheptyl, phenyl and pentadeuterated phenyl.

Preferably, the formula a is selected from one of the following groups:

the formula b is selected from one of the following groups:

the formula c is selected from one of the following groups:

preferably, said R is₀、R₁、R₂、R₃、R₄Are identical or different from each other and are each independently selected from hydrogen, deuterium, a halogen atom, cyano, methyl, ethylN-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, phenyl-naphthyl, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, carbazolyl, 9-phenylcarbazolyl, pyrenyl, indolyl, acridinyl, pyridyl, furyl, thienyl, benzothienyl, benzofuryl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzothienyl, dibenzofuryl, phenothiazinyl, phenoxazinyl, deuteroadamantyl, deuteronorbornyl, deuterophenyl, deuteronaphthyl, deuterobiphenyl, deuteroterphenyl, deuteroanthracenyl, deuterophenanthrenyl, deuterotriphenylenyl, deuterofluorenyl, and the like, One of deuterated phenyl-naphthyl, deuterated phenyl-deuterated naphthyl, deuterated dibenzothienyl, deuterated dibenzofuranyl, deuterated 9, 9-dimethylfluorenyl, deuterated 9, 9-diphenylfluorenyl and deuterated spirobifluorenyl, or adjacent R₀Adjacent R₁Adjacent R₂Adjacent R₃Adjacent R₄Can be connected into a ring structure.

Preferably, said R is₁、R₂Independently selected from one or more of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylenyl, deuterated dibenzothienyl, deuterated dibenzofuranyl, deuterated 9, 9-dimethylfluorenyl, deuterated 9, 9-diphenylfluorenyl, deuterated spirobifluorenyl, or adjacent R₁Adjacent R₂May be bonded to form a cyclic structure, and when substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Preferably, R is selected from one of methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl, norbornyl, phenyl, pentadeuterated phenyl, deuterated naphthyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl, deuterated anthryl, deuterated phenanthryl, deuterated triphenylenyl, deuterated dibenzothienyl, deuterated dibenzofuranyl, deuterated 9, 9-dimethylfluorenyl, deuterated 9, 9-diphenylfluorenyl, and deuterated spirobifluorenyl.

More preferably, theOne selected from the following groups:

preferably, said L₀、L₁、L₂、L_mIndependently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted 9, 9-dimethylfluorenyl, substituted or unsubstituted 9, 9-diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted triphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9-phenylcarbazolyl, substituted or unsubstituted benzoxadiazolyl, substituted or unsubstituted benzothiadiazolyl, substituted or unsubstituted phenylene-naphthylene, wherein the substituent is deuterium, methyl, ethyl, isopropyl, or a mixture thereof, One or more of tert-butyl, phenyl and pentadeuterophenyl, wherein when substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other.

Preferably, said L₀、L₁、L₂、L_mIndependently selected from a single bond or one of the following groups:

more preferably, said L₀、L₁、L₂、L_mIndependently selected from a single bond or one of the following groups:

preferably, said R is₀、R₃、R₄The same or different from each other, and each is independently selected from hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, or one of the groups shown below:

more preferably, R is₀、R₃、R₄The same or different from each other, and each is independently selected from hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, or one of the groups shown below:

most preferably, the triarylamine compound is selected from any one of the following chemical structures:

the triarylamine compound of formula I of the present invention can be prepared by conventional coupling reactions in the art, for example, by the following synthetic routes, but the present invention is not limited thereto:

the invention relates to a preparation method of triarylamine compound shown in formula I, firstly preparing raw material c-, namely, under nitrogen atmosphere, amine compound a and halogen compound b are reacted by Buhwald to obtain raw material c-; then preparing an intermediate A, namely obtaining a lithium compound by a lithium reaction of a double-halogen compound a-in the environment of n-butyllithium, and simultaneously reacting the lithium compound with a compound b-to obtain the intermediate A; the intermediate A and the raw material c-are subjected to a Buchwald reaction and react under a corresponding catalyst, an organic base, a ligand, a solution and a corresponding temperature to obtain the compound shown in the formula I, wherein B₀、B₁、B₂Represents Cl, Br or I.

Alternatively, the intermediate A can be converted into another intermediate A by Suzuki reaction, and then subjected to Buhward reaction with the raw material c-, and reacted under corresponding catalyst, organic base, ligand, solution and corresponding temperature to obtain the compound of formula I, wherein B₀、B₁、B₂Represents Cl, Br or I.

The present invention is not particularly limited in terms of the source of the raw materials used in the above-mentioned various reactions, and can be obtained using commercially available raw materials or by a preparation method known to those skilled in the art. The present invention is not particularly limited to the above-mentioned reaction, and a conventional reaction known to those skilled in the art may be used. The compound provided by the invention has the advantages of few synthesis steps and simple method, and is beneficial to industrial production.

The invention also provides an organic light-emitting device which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or positioned outside more than one of the anode and the cathode, and the organic layer contains any one or the combination of at least two of the triarylamine compounds.

Preferably, the organic layer comprises a hole transport layer containing any one or a combination of at least two of the triarylamine compounds described in the present invention.

Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, and the first hole transport layer and/or the second hole transport layer contains any one or a combination of at least two of the triarylamine compounds described in the present invention.

Preferably, the organic layer includes a capping layer containing any one or a combination of at least two of the triarylamine compounds described in the present invention.

Preferably, the capping layer according to the present invention may have a single-layer structure, a two-layer structure or a multi-layer structure, and the capping layer material according to the present invention may have at least one selected from the triarylamine compounds according to the present invention, or may include a conventional capping layer material known to those skilled in the art.

Preferably, the organic light emitting device of the present invention is selected from the following structures, but is not limited thereto:

(1) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;

(2) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode;

(3) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/hole blocking layer/cathode;

(4) anode/hole transport layer/light emitting layer/electron transport layer/cathode;

(5) anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(6) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode;

(7) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(8) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/cathode;

(9) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(10) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(11) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(12) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(13) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(14) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode;

(15) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(16) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode;

(17) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(18) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode/capping layer;

(19) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(20) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(21) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(22) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(23) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode/capping layer;

(24) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(25) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

(26) anode/hole injection layer/hole buffer layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(27) anode/hole injection layer/hole buffer layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

(28) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode;

(29) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron injection layer/cathode;

(30) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;

(31) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode;

(32) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron injection layer/cathode;

(33) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode/capping layer;

(34) anode/hole injection layer/hole transport layer/light emitting layer/cathode/capping layer;

(35) anode/hole injection layer/hole transport layer/light emitting layer/cathode;

(36) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/cathode;

(37) anode/hole injection layer/first hole transport layer/second hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode/capping layer;

(38) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;

(39) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode;

(40) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode;

(41) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/an electron transport layer/a cathode;

(42) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

(43) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/cathode;

(44) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(45) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/cathode;

(46) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode;

(47) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;

(48) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

(49) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;

(50) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

(51) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/a cathode;

(52) an anode/a first hole transport layer/a second hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;

(53) anode/hole injection layer/first hole transport layer/second hole transport layer/luminescent layer/hole blocking layer/electron transport layer/cathode;

(54) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;

(55) anode/hole injection layer/first hole transport layer/second hole transport layer/luminescent layer/hole blocking layer/electron transport layer/cathode/capping layer;

(56) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;

(57) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

(58) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/a cathode;

(59) an anode/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/an electron transport layer/an electron injection layer/a cathode;

(60) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/cathode/capping layer;

(61) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;

(62) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode/a capping layer;

(63) an anode/a hole injection layer/a hole buffer layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode;

(64) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

(65) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode;

(66) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/electron injection layer/cathode;

(67) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;

(68) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/a cathode;

(69) an anode/a hole injection layer/a first hole transport layer/a second hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron injection layer/a cathode;

(70) anode/hole injection layer/first hole transport layer/second hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode/capping layer;

(71) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/cathode/capping layer;

(72) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/cathode;

(73) anode/hole injection layer/hole buffer layer/first hole transport layer/second hole transport layer/light emitting layer/cathode;

(74) anode/hole injection layer/first hole transport layer/second hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer.

However, the structure of the organic light emitting device is not limited thereto. The organic light-emitting device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, and part of organic layers can be added or omitted. For example, an electron buffer layer can be added between the electron transport layer and the electron injection layer; the organic layer having the same function may be formed in a stacked structure of two or more layers, for example, the electron transport layer may have a first electron transport layer and a second electron transport layer.

The light emitting device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.

The anode material is preferably a material having a large work function so that holes are smoothly injected into the organic material layer, and a conductive metal oxide film, a translucent metal thin film, or the like is often used. For example, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used.

The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).

The material of the hole transport region may be selected from small molecular materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and polymer materials such as poly-p-phenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinylcarbazole and its derivatives, polysilane and its derivatives, but is not limited thereto. Preferably, the hole transport layer of the present invention is selected from the group consisting of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB), N '-di (naphthalene-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (abbreviated as. alpha. -NPD), N' -diphenyl-N, N '-di (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (abbreviated as TPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetra (diphenylamino) -9, 9-spirobifluorene (short for: Spiro-TAD) and the like can be a single structure formed by a single substance, or a single-layer structure or a multi-layer structure formed by different substances, and preferably, the hole transport layer is any one or a combination of at least two of the triarylamine compounds. The material of the hole transport region may include a first hole transport layer material and a second hole transport layer material.

The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole-injecting layer may employ one or more compounds of the above-mentioned H-1 to H-12, or employ one or more compounds of HI1-HI2 described below; one or more of the compounds H-1 to H-12 may also be used to dope one or more of the compounds HI1-HI2 described below. In addition to the above materials, the hole injection layer material may also include other known materials suitable for the light emitting layer;

the electron blocking layer material may be selected from N, N ' -bis (naphthalene-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (abbreviated as α -NPD), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (abbreviated as TPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviated as Spiro-TAD), etc., which may be a single structure composed of a single substance, and may be a single-layer structure or a multi-layer structure formed of different substances.

The light-emitting layer includes a light-emitting material (i.e., Dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.

According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an organic light emitting device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.

In the light-emitting layer of the organic light-emitting device of the present invention, a red light-emitting material, a green light-emitting material, or a blue light-emitting material can be used as the light-emitting material, and two or more light-emitting materials can be mixed if necessary. The light-emitting material may be a host material alone or a mixture of a host material and a dopant material, and the light-emitting layer is preferably formed using a mixture of a host material and a dopant material.

Preferably, the host material of the present invention is selected from 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1": 4', 1' -tetrabiphenyl ] -4,4' -diamino (4PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like. In addition to the above materials and combinations thereof, the light emitting layer host material may also include other known materials suitable for use as a light emitting layer, such as the following light emitting layer host materials:

the blue luminescent layer guest is selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA for short), 2,5,8, 11-tetra-tert-butylperylene (TBPe for short), 4' -di [4- (diphenylamino) styryl group]Biphenyl (BDAVBi for short), 4' -di [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi for short), bis (2-hydroxyphenyl pyridine) beryllium (Bepp for short)₂) Bis (4, 6-difluorophenylpyridine-C2, N) picolinyliridium (FIrpic), and the like, and in addition to the above materials and combinations thereof, the guest material of the blue light-emitting layer may further include other known materials suitable for use as a light-emitting layer. The green emissive guest layer is selected from tris (2-phenylpyridine) iridium (Ir (ppy)₃) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy)₂(acac)), etc., the green light-emitting layer guest material can include other known materials suitable for use as a light-emitting layer in addition to the above materials and combinations thereof. The red light emitting layer guest can be selected from 9, 10-di [ N- (p-tolyl) anilino]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq)₃) Bis (1-phenylisoquinoline) (acetylacetonato) iridium (Ir (piq))₂(acac)) and the like. In addition to the above materials, the red light-emitting layer guest material may also include other known materials suitable for use as a light-emitting layer.

The doping ratio of the host material and the guest material of the light-emitting layer may be preferably varied depending on the materials used, and the doping percentage of the guest material of the light-emitting layer is usually 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

The electron transport region is located between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).

The electron transport layer may include a first electron transport layer material and a second electron transport layer material. Commonly used materials for the electron transport material are known metal complexes of oxadiazole derivatives, anthraquinone dimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinone dimethane and derivatives thereof, fluorenone derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and derivatives thereof, which can be single structures formed by single substances or single-layer structures or multi-layer structures formed by different substances.

The electron injection layer is located between the electron transport layer and the cathode, and the electron injection layer is made of one or more of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, and Ca, but not limited thereto

The hole blocking layer material can be selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tri (N-phenyl-2-benzimidazole) benzene (TPBi), and tri (8-hydroxyquinoline) aluminum (III) (Alq)₃) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

As the cathode material, a metal material having a small work function is generally preferred. For example, metals or alloys of magnesium (Mg), silver (Ag), aluminum (a1), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and any combination thereof may be used. Among them, when light emission of the light-emitting layer is extracted from the cathode, the light transmittance of the cathode is preferably more than 10%. It is also preferable that the sheet resistivity of the cathode is several hundred Ω/□ or less, and the film thickness is usually 10nm to 1 μm, preferably 50 to 200 nm.

Alq can be used as the cover material of the invention₃TPBi or the triarylamine compound described in the invention or the combination of at least two of the TPBi and the triarylamine compound. Preferably, the material of the cover layer is selected from any one or at least two of the organic compounds for the cover layer according to the inventionAnd (4) combining.

The film thicknesses of the hole transporting layer and the electron transporting layer may be selected as appropriate depending on the materials used, and may be selected so as to achieve appropriate values of the driving voltage and the light emission efficiency. Therefore, the film thicknesses of the hole transporting layer and the electron transporting layer are, for example, 1nm to 1um, preferably 2nm to 500nm, and more preferably 5nm to 200 nm.

The order and number of layers to be stacked and the thickness of each layer can be appropriately selected in consideration of the light emission efficiency and the lifetime of the device.

The method for forming each layer in the organic light-emitting device is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray, slit coating, and dip coating may be used, and in the present invention, vacuum evaporation is preferably used. The compounds used as the organic layer may be small organic molecules, large organic molecules, and polymers, and combinations thereof.

The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.

Preparation and characterization of the Compounds

Description of raw materials, reagents and characterization equipment:

the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.

The mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;

the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;

synthesis example 1 Synthesis of Compound 4

Synthesis of starting Material c-4

Under nitrogen protection, a4(4.42g, 45mmol), b4(16.44g, 45mmol), palladium acetate (0.16g, 0.7mmol), sodium tert-butoxide (7.69g, 80mmol), tri-tert-butylphosphine (3mL of a 1.0M solution in toluene) and 500mL of toluene were added to a reaction flask and reacted for 2h under reflux. After the reaction was completed, the mixture was cooled to room temperature, filtered through celite, the filtrate was rotary evaporated to remove the solvent, and then recrystallized through toluene to obtain a recrystallized solid, i.e., c-4(13.43g, yield 78%), by suction filtration. Mass spectrum m/z: 382.2442 (theoretical value: 382.2457).

Synthesis of intermediate A-4

A-4(11.26g, 40mmol), tetrahydrofuran (200mL) and n-butyllithium (25mL of 1.6M in hexane) were added to a reaction flask under nitrogen and the reaction stirred at-78 deg.C for 50 min. Then, a tetrahydrofuran solution (80mL) containing b-4(10.33g, 40mmol) was added dropwise to the reaction flask, and the reaction was stirred at-78 ℃ for 50min and then at room temperature for 4 h. After the reaction was complete, saturated ammonium chloride solution was added, the organic layer was separated and the solvent was removed by rotary evaporation. The residual solid, acetic anhydride (400mL) and hydrochloric acid (15mL) were charged into a reaction flask, and the reaction was stirred at 100 ℃ for 3.5h, after completion of the reaction, cold water (150mL) was added to precipitate a solid product and the solid product was filtered, followed by purification on a silica gel column (petroleum ether/dichloromethane ═ 10: 1) to obtain intermediate a-4(14.71g, yield 83%). Mass spectrum m/z: 442.1135 (theoretical value: 442.1124).

Synthesis of Compound 4

Under the protection of nitrogen, intermediate A-4(13.29g, 30mmol), c-4(11.48g, 30mmol), palladium acetate (0.11g, 0.47mmol) and tert-butyl alcohol are addedSodium (5.10g, 53mmol), tri-tert-butylphosphine (2.8mL of a 1.0M solution in toluene) and 450mL of toluene were added to the reaction flask and the reaction was heated for 6 h. After the reaction was completed, the reaction mixture was cooled to normal temperature, ice water was added to precipitate a solid product, the solid product was filtered, and the collected solid was purified by a silica gel column (petroleum ether/ethyl acetate: 8: 1) to obtain compound 4(19.17g, yield 81%) with a solid purity of 99.87% or more by HPLC. Mass spectrum m/z: 788.3802 (theoretical value: 788.3815). Theoretical element content (%) C₅₉H₄₀D₅NO: c, 89.81; h, 6.39; n, 1.78. Measured elemental content (%): c, 89.85; h, 6.37; n, 1.73.

Synthesis example 2 Synthesis of Compound 8

Compound 8(21.30g) was synthesized in the same manner as in Synthesis example 1, except that a4 was replaced with an equimolar amount of a8 and a-4 was replaced with an equimolar amount of a-8, and the purity of the solid was determined by HPLC (HPLC) and was 99.85% or more. Mass spectrum m/z: 909.3963 (theoretical value: 909.3971). Theoretical element content (%) C₆₉H₅₁NO: c, 91.06; h, 5.65; n, 1.54. Measured elemental content (%): c, 91.03; h, 5.67; n, 1.57.

Synthesis example 3 Synthesis of Compound 11

Compound 11(22.67g) was synthesized using the same procedure as that used for the synthesis of Compound 4 in Synthesis example 1, except that a4 was replaced with an equimolar amount of a11 and a-4 was replaced with an equimolar amount of a-11, and the purity of the solid was determined by HPLC (HPLC) to be 99.87% or higher. Mass spectrum m/z: 883.3822 (theoretical value: 883.3814). Theoretical element content (%) C₆₇H₄₉NO: c, 91.02; h, 5.59; n, 1.58. Measured elemental content (%): c, 91.05; h, 5.57; n, 1.63.

Synthesis example 4 Synthesis of Compound 22

Compound 22(22.41g) was synthesized using the same method as that used for the synthesis of Compound 4 in Synthesis example 1 except that a4 was replaced with an equimolar amount of a22, and the purity of the solid was ≧ 99.79% by HPLC. Mass spectrum m/z: 899.4115 (theoretical value: 899.4127). Theoretical element content (%) C₆₈H₅₃NO: c, 90.73; h, 5.93; n, 1.56. Measured elemental content (%): c, 90.72; h, 5.97; n, 1.53.

Synthesis example 5 Synthesis of Compound 29

The same procedure as used for the synthesis of Compound 4 in Synthesis example 1 was carried out in which a4 was replaced with an equivalent mole of a29 and a-4 was replaced with an equivalent mole of a-29 to synthesize Compound 29(23.66g) with a solid purity of 99.88% or more by HPLC. Mass spectrum m/z: 1023.4431 (theoretical value: 1023.4440). Theoretical element content (%) C₇₈H₅₇NO: c, 91.46; h, 5.61; n, 1.37. Measured elemental content (%): c, 91.49; h, 5.63; n, 1.36.

Synthesis example 6 Synthesis of Compound 38

Compound 38(23.48g, 69% yield) was synthesized using the same procedure as that used for the synthesis of compound 4 in synthesis example 1, except that a4 was replaced with an equimolar amount of a38, and the purity of the solid was ≧ 99.81% by HPLC. Mass spectrum m/z: 1133.5543 (theoretical value: 1133.5536). Theoretical element content (%) C₈₆H₇₁NO: c, 91.05; h, 6.31; n, 1.23. Measured elemental content (%): c, 91.07; h, 6.36; n, 1.26.

Synthesis example 7 Synthesis of Compound 58

Synthesis of raw Material c-58 the same procedure as for the synthesis of raw material c-4 in Synthesis of Compound 4 of example 1 was conducted, except that a4 was replaced with equimolar a58 to synthesize raw material c-58.

Synthesis of starting Material B-4

Under the protection of nitrogen, the intermediate A-4(46.06g, 104mmol), b58(29.05g, 114.4mmol), potassium acetate (30.6g, 312mmol), 1,1' -bis-diphenylphosphino ferrocene palladium dichloride (2.4g, 3.2mmol) and N, N-dimethylformamide (500mL) are added into a reaction flask in sequence, then placed in an oil bath at 85 ℃ for reaction for 5h, cooled to room temperature, added with 600mL of water, filtered, washed with water and dried. The resulting precipitate was dissolved in 500mL of ethyl acetate. Then, insoluble matter was removed by filtration, the filtrate was collected, the solvent was removed by rotary evaporation, and the residual solid was separated and purified by a silica gel column (petroleum ether: ethyl acetate ═ 2:1), and dried to obtain intermediate B-4(45.02g, yield 81%). Mass spectrum m/z: 534.2353 (theoretical value: 534.2366).

Synthesis of intermediate A-58

D58(9.68g, 49.52mmol), intermediate B-4(25.95g, 48.56mmol), tetrakistriphenylphosphine palladium (0.56g, 0.48mmol), potassium acetate (7.14g, 72.83mmol) and 150mL of toluene, 75mL of ethanol and 75mL of water were added to a reaction flask in this order under an argon atmosphere, and the mixture was stirred and the system was refluxed for 4.5 hours; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol: 2 to yield intermediate a-58(20.32g, 80% yield). Mass spectrum m/z: 522.1673 (theoretical value: 522.1689).

Synthesis of Compound 58

Compound 58(24.09g, 76% yield) was synthesized using the same procedure as that used for the synthesis of compound 4 in synthesis example 1, except that c-4 was replaced with an equivalent mole of c-58 and intermediate a-4 was replaced with an equivalent mole of a-58, and the purity of the solid was ≧ 99.85% by HPLC. Mass spectrum m/z: 1055.5016 (theoretical value: 1055.5004). Theoretical element content (%) C₈₀H₅₇D₄NO: c, 90.96; h, 6.20; n, 1.33. Measured elemental content (%): c, 90.93; h, 6.24; n, 1.36.

Synthesis example 8 Synthesis of Compound 73

Compound 73(22.37g) was synthesized using the same method as that used for the synthesis of Compound 4 in Synthesis example 1 except that a4 was replaced with an equimolar amount of a73, and the purity of the solid was ≧ 99.86% by HPLC. Mass spectrum m/z: 980.4762 (theoretical value: 980.4754). Theoretical element content (%) C₇₄H₅₂D₅NO: c, 90.57; h, 6.37; n, 1.43. Measured elemental content (%): c, 90.55; h, 6.32; n, 1.46.

Synthesis example 9 Synthesis of Compound 79

The same procedure as used for the synthesis of Compound 4 in Synthesis example 1 was carried out in the same manner except that a4 was replaced with equal moles of a79 and a-4 was replaced with equal moles of a-79 to synthesize Compound 79(22.28g) with a solid purity of 99.89% or more by HPLC. Mass spectrum m/z: 989.4585 (theoretical value: 989.4597). Theoretical element content (%) C₇₅H₅₉NO: c, 90.96; h, 6.01; n, 1.41. Measured elemental content (%): c, 90.93; h, 6.05; n, 1.43.

Synthesis example 10 Synthesis of Compound 99

Compound 99(23.94g) was synthesized using the same procedure as that used for the synthesis of Compound 4 in Synthesis example 1, except that a4 was replaced with an equimolar amount of a99, and the purity of the solid was ≧ 99.87% by HPLC. Mass spectrum m/z: 1155.5393 (theoretical value: 1155.5379). Theoretical element content (%) C₈₈H₆₉NO: c, 91.39; h, 6.01; n, 1.21. Measured elemental content (%): c, 91.36; h, 6.06; and N, 1.24.

Synthesis example 11 Synthesis of Compound 106

Compound 106(23.53g) was synthesized using the same method as that used for the synthesis of Compound 4 in Synthesis example 1 except that a4 was replaced with an equimolar amount of a106, and the purity of the solid was ≧ 99.84% by HPLC. Mass spectrum m/z: 1073.4584 (theoretical value: 1073.4597). Theoretical element content (%) C₈₂H₅₉NO: c, 91.67; h, 5.54; and N, 1.30. Measured elemental content (%): c, 91.64; h, 5.56; n, 1.35.

Synthesis example 12 Synthesis of Compound 148

Compound 148(21.12g) was synthesized in the same manner as in Synthesis example 1, except that a4 was replaced with an equimolar amount of a148 and a-4 was replaced with an equimolar amount of a-148, whereby Compound 4 was synthesized with a solid purity of 99.86% or more by HPLC. Mass spectrum m/z: 913.4235 (theoretical value: 913.4222). Theoretical element content (%) C₆₉H₄₇D₄NO: c, 90.65; h, 6.06; n, 1.53. Measured elemental content (%): c, 90.63; h, 6.09; n, 1.57.

Synthesis example 13 Synthesis of Compound 157

The same procedure as used in Synthesis example 1, in which a4 was replaced with an equivalent mole of a157 and a-4 was replaced with an equivalent mole of a-11, was used to synthesize compound 157(22.78g) having a solid purity of 99.79% or more by HPLC. Mass spectrum m/z: 1025.4248 (theoretical value: 1025.4233). Theoretical element content (%) C₇₇H₅₅NO₂: c, 90.12; h, 5.40; n, 1.36. Actually measured element content (%) C, 90.15; h, 5.42; and N, 1.40.

Synthesis example 14 Synthesis of Compound 187

Synthesis of Compound 187

Compound 187(22.80g) was synthesized in the same manner as in Synthesis of Compound 58 in EXAMPLE 7, except that a58 was replaced with an equivalent mole of a187 and d58 was replaced with an equivalent mole of a-11, and the purity of the solid was ≧ 99.83% by HPLC. Mass spectrum m/z: 949.3933 (theoretical value: 949.3920). Theoretical element content (%) C₇₁H₅₁NO₂: c, 89.75; h, 5.41; and N, 1.47. Measured elemental content (%): c, 89.77; h, 5.43; n, 1.48.

Synthesis example 15 Synthesis of Compound 198

The same procedure as used for the synthesis of compound 4 in Synthesis example 1, wherein a4 was replaced with an equivalent mole of a198 and a-4 was replaced with an equivalent mole of a-198, was used to synthesize compound 198(23.19g) with a solid purity ≧ 99.83% by HPLC. Mass spectrum m/z: 1103.5235 (theoretical value: 1103.5227). Theoretical element content (%) C₈₄H₅₇D₅N₂: c, 91.35; h, 6.11; and N, 2.54. Measured elemental content (%): c, 91.38; h, 6.13; and N, 2.57.

Synthesis example 16 Synthesis of Compound 217

The same procedure as used for the synthesis of Compound 4 in Synthesis example 1 was carried out in which compound 217(22.61g) was synthesized by substituting a4 with an equivalent mole of a217 and a-4 with an equivalent mole of a-217, and the purity of the solid was ≧ 99.87% by HPLC. Mass spectrum m/z: 1107.4818 (theoretical value: 1107.4804). Theoretical element content (%) C₈₆H₆₁N: c, 93.19; h, 5.55; n, 1.26. Measured elemental content (%): c, 93.20; h, 5.53; n, 1.28.

[ Synthesis example 17] Synthesis of Compound 227

The same procedure as that used for the synthesis of compound 4 in Synthesis example 1 was repeated except that a4 was replaced with an equimolar amount of a227 to synthesize compound 227(21.63g) and the purity of the solid was ≧ 99.86% by HPLC. Mass spectrum m/z: 923.3775 (theoretical value: 923.3763). Theoretical element content (%) C₆₉H₄₉NO₂: c, 89.68; h, 5.34; n, 1.52. Measured elemental content (%): c, 89.69; h, 5.39; n, 1.54.

Synthesis example 18 Synthesis of Compound 234

Compound 234(21.95g) was synthesized by the same method as that used for synthesizing compound 4 in synthesis example 1 except that a4 was replaced with an equimolar amount of a234, and the purity of the solid was ≧ 99.85% by HPLC. Mass spectrum m/z: 949.3936 (theoretical value: 949.3920). Theoretical element content (%) C₇₁H₅₁NO₂: c, 89.75; h, 5.41; and N, 1.47. Measured elemental content (%): c, 89.76; h, 5.46; n, 1.49.

Synthesis example 19 Synthesis of Compound 266

The same procedure as used in Synthesis example 1, in which a4 was replaced with an equal mole of a266 and a-4 was replaced with an equal mole of a-266, was used to synthesize 266(21.21g) having a solid purity of 99.87% or more by HPLC. Mass spectrum m/z: 905.3162 (theoretical value: 905.3150). Theoretical element content (%) C₆₅H₄₇NS₂: c, 86.15; h, 5.23; n, 1.55. Measured elemental content (%): c, 86.19; h, 5.25; n, 1.57.

Synthesis example 20 Synthesis of Compound 280

The same procedure as that used for the synthesis of Compound 4 in Synthesis example 1 was used, except that a4 was replaced with an equivalent mole of a280 and a-4 was replaced with an equivalent mole of a-280, to synthesize Compound 280(22.81g) with a solid purity ≧ 99.79% by HPLC. Mass spectrum m/z: 1040.4175 (theoretical value: 1040.4164). Theoretical element content (%) C₇₇H₅₆N₂S: c, 88.81; h, 5.42; and N, 2.69. Measured elemental content (%): c, 88.83; h, 5.43; n, 2.73.

Synthesis example 21 Synthesis of Compound 288

The same procedure as used for the synthesis of compound 4 in synthesis example 1 was used, except that a4 was replaced with equimolar a288, b4 was replaced with equimolar b288, and a-4 was replaced with equimolar a-280, to synthesize compound 288(22.26g) with a solid purity of 99.83% by HPLC. Mass spectrum m/z: 975.4202 (theoretical value: 975.4189). Theoretical element content (%) C₇₂H₅₃N₃O: c, 88.58; h, 5.47; and N, 4.30. Measured elemental content (%): c, 88.59; h, 5.50; and N, 4.28.

Synthesis example 22 Synthesis of Compound 296

The same procedure as that used for the synthesis of compound 4 in Synthesis example 1, wherein a4 was replaced with an equimolar amount of a296, was used to synthesize compound 296(21.09g) having a purity of 99.87% by HPLC. Mass spectrum m/z: 900.3728 (theoretical value: 900.3716). Theoretical element content (%) C₆₆H₄₈N₂O₂: c, 87.97; h, 5.37; n, 3.11. Measured elemental content (%): c, 87.92; h, performing a chemical reaction on the mixture of the hydrogen peroxide and the nitrogen peroxide,5.39；N,3.17。

synthesis example 23 Synthesis of Compound 301

Compound 301(20.84g) was synthesized using the same method as that used for the synthesis of compound 4 in synthesis example 1, except that a4 was replaced with an equimolar amount of a301, and the solid purity by HPLC ≧ 99.86% was used. Mass spectrum m/z: 901.3679 (theoretical value: 901.3668). Theoretical element content (%) C₆₅H₄₇N₃O₂: c, 86.54; h, 5.25; and N, 4.66. Measured elemental content (%): c, 86.55; h, 5.29; and N, 4.63.

Synthesis example 24 Synthesis of Compound 308

Compound 308(21.71g) was synthesized in the same manner as in Synthesis example 1, except that a4 was replaced with equimolar a308 and a-4 was replaced with equimolar a-308, and that the purity of the solid was 99.78% or more by HPLC. Mass spectrum m/z: 1063.4766 (theoretical value: 1063.4753). Theoretical element content (%) C₈₁H₆₁NO: c, 91.40; h, 5.78; n, 1.32. Measured elemental content (%): c, 91.38; h, 5.79; n, 1.36.

[ Synthesis example 25] Synthesis of Compound 319

Compound 319(22.14g) was synthesized by the same method as that for the synthesis of Compound 4 in Synthesis example 1 except that a4 was changed to equal moles of a319, and the purity of the solid was ≧ 99.76% by HPLC. Mass spectrum m/z: 1053.4017 (theoretical value: 1053.4004). Theoretical element content (%) C₇₈H₅₅NOS: c, 88.86; h, 5.26; n, 1.33. Measured elemental content (%): c, 88.87; h, 5.29; n, 1.35.

[ Synthesis example 26] Synthesis of Compound 347

Compound 347(22.80g) was synthesized in the same manner as in the synthesis of compound 4 in synthetic example 1 except that a4 was replaced with an equivalent mole of a347 and b4 was replaced with an equivalent mole of b347, and the solid purity by HPLC was ≧ 99.77%. Mass spectrum m/z: 1069.5239 (theoretical value: 1069.5223). Theoretical element content (%) C₈₁H₆₇NO: c, 90.89; h, 6.31; n, 1.31. Measured elemental content (%): c, 90.90; h, 6.36; n, 1.35.

Synthesis example 27 Synthesis of Compound 386

The same procedure as that used for the synthesis of Compound 4 in Synthesis example 1 was carried out in the same manner except that a4 was replaced with an equal mole of a386 and a-4 was replaced with an equal mole of a-266 to synthesize Compound 386(20.62g) with a solid purity of 99.89% or more by HPLC. Mass spectrum m/z: 880.3915 (theoretical value: 880.3900). Theoretical element content (%) C₆₅H₄₄D₅And NS: c, 88.60; h, 6.18; n, 1.59. Measured elemental content (%): c, 88.62; h, 6.23; n, 1.61.

Synthesis example 28 Synthesis of Compound 412

Compound 412(19.44g) was synthesized in the same manner as in Synthesis example 1, except that a4 was replaced with an equimolar amount of a412, a-4 was replaced with an equimolar amount of a-266, and b-4 was replaced with an equimolar amount of b-412, and that the purity of the solid was 99.88% or more by HPLC. Mass spectrum m/z: 819.39013 (theoretical value: 819.3899). Theoretical element content (%) C₆₀H₅₃And NS: c, 87.87; h, 6.51; n, 1.71. Measured elemental content (%):C,87.88；H,6.48；N,1.76。

synthesis example 29 Synthesis of Compound 440

Compound 440(23.35g) was synthesized in the same manner as in Synthesis example 1, except that a4 was replaced with an equivalent mole of a440 and a-4 was replaced with an equivalent mole of a-440, and that the purity of the solid was 99.79% or more by HPLC. Mass spectrum m/z: 1023.4568 (theoretical value: 1023.4552). Theoretical element content (%) C₇₇H₅₇N₃: c, 90.29; h, 5.61; and N, 4.10. Measured elemental content (%): c, 90.22; h, 5.64; and N, 4.15.

[ Synthesis example 30] Synthesis of Compound 451

Compound 451(22.74g) was synthesized by the same method as that for the synthesis of Compound 4 in Synthesis example 1, except that a4 was replaced with an equivalent mole of a451 and a-4 was replaced with an equivalent mole of a-280, and the purity of the solid was 99.78% or more by HPLC. Mass spectrum m/z: 1066.5237 (theoretical value: 1066.5226). Theoretical element content (%) C₈₁H₆₆N₂: c, 91.14; h, 6.23; and N, 2.62. Measured elemental content (%): c, 91.15; h, 6.25; and N, 2.60.

[ Synthesis example 31] Synthesis of Compound 469

Compound 469(23.03g) was synthesized using the same procedure as that used for the synthesis of compound 58 in synthetic example 7, except that a58 was replaced with an equimolar amount of intermediate a22, b4 was replaced with an equimolar amount of b288, a-4 was replaced with an equimolar amount of a-280, and d58 was replaced with an equimolar amount of d469, and the purity of solid was 99.79% by HPLC. Mass spectrum m/z: 1050.4927 (theoretical value: 1050.4913). Theory of thingsArgument content (%) C₈₀H₆₂N₂: c, 91.39; h, 5.94; and N, 2.66. Measured elemental content (%): c, 91.40; h, 5.98; and N, 2.68.

Synthesis example 32 Synthesis of Compound 474

The same procedure as that used for the synthesis of Compound 4 in Synthesis example 1 was repeated except that a4 was replaced with an equivalent mole of a474 and a-4 was replaced with an equivalent mole of a-474 to synthesize Compound 474(23.27g) with a solid purity of 99.81% or more by HPLC. Mass spectrum m/z: 1033.5366 (theoretical value: 1033.5352). Theoretical element content (%) C₇₈H₅₅D₇N₂: c, 90.57; h, 6.72; n, 2.71. Measured elemental content (%): c, 90.60; h, 6.73; and N, 2.68.

Synthesis example 33 Synthesis of Compound 505

Compound 505(23.18g) was synthesized by the same method as that for the synthesis of compound 4 in synthesis example 1, except that a4 was replaced with an equimolar amount of a505, b4 was replaced with an equimolar amount of b505, and a-4 was replaced with an equimolar amount of a-505, and the purity of the solid was 99.80% by HPLC. Mass spectrum m/z: 1057.4659 (theoretical value: 1057.4648). Theoretical element content (%) C₈₂H₅₉N: c, 93.06; h, 5.62; n, 1.32. Measured elemental content (%): c, 93.07; h, 5.64; n, 1.29.

Red organic luminescent device (hole transport layer)

Comparative examples 1-2 device preparation examples:

comparative example 1: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.

Evaporating a hole injection layer m-MTDATA/19nm, a hole transport layer HT-1/83nm and an evaporation main body H-8 on the prepared ITO transparent electrode in a layer-by-layer vacuum evaporation mode: h-13: doped Ir (dpm) PQ2 (49%: 49%: 2% mixed) mix/21 nm and then evaporated with an electron transport layer Alq₃Liq (doping ratio is 1:1)/23nm, an electron injection layer LiF/1nm and a cathode Al/121 nm. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:

comparative example 2: the hole transport layer material HT-1 in comparative example 1 was replaced with HT-2, and an organic light emitting device of comparative example 2 was fabricated in the same manner as in comparative example 1.

Comparative example 3: the hole transport layer material HT-1 in comparative example 1 was changed to HT-3, and an organic light emitting device of comparative example 3 was fabricated in the same manner as in comparative example 1.

[ examples 1 to 26]

Examples 1 to 26: the hole transport layer material HT-1 of the organic light emitting device was sequentially changed to the compounds 4, 8, 22, 29, 38, 58, 73, 79, 99, 110, 148, 187, 198, 234, 280, 288, 308, 319, 347, 368, 412, 440, 451, 469, 474, 505 of the present invention, and the other steps were the same as in comparative example 1.

The test software, computer, K2400 digital source manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic light emitting device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.

Table 1 test of light emitting characteristics of light emitting device

Note: t95 denotes a current density of 10mA/cm²In this case, the time taken for the luminance of the device to decay to 95%;

as can be seen from the results in table 1, the triarylamine compound of the present invention, when applied to an organic light emitting device as a hole transport layer material, exhibits the advantage of higher luminous efficiency compared to comparative examples 1 to 3, and is a hole transport material for an organic light emitting device with good performance.

Green organic light emitting device (second hole transport layer)

Comparative examples 4-6 device preparation examples:

comparative example 4: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO transparent substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, drying, and conveying to an evaporation plating machine.

Evaporating hole injection layer (H1: HI1 (97%: 3%))/19 nm, first hole transport layer HT1/86nm, second hole transport layer HT2-1/42nm, and luminescent layer (host H-2: H-5: Ir (mppy)) on prepared ITO transparent substrate by layer-by-layer vacuum evaporation₃(49%: 49%: 2% mixed))/21 nm, and then evaporating an electron transport layer ET-1 and Liq (the doping ratio is 1:1)/23nm, an electron injection layer LiF/0.5nm and a cathode Al/119 nm. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the fabrication of the organic light emitting device is completed according to the above steps, the device is measuredThe photoelectric property and the molecular structural formula of the related material are shown as follows:

comparative example 5: the organic light emitting device of comparative example 5 was fabricated in the same manner as in comparative example 4, except that the second hole transport layer material HT2-1 in comparative example 4 was changed to HT 2-2.

Comparative example 6: the organic light emitting device of comparative example 6 was fabricated in the same manner as in comparative example 4, except that the second hole transport layer material HT2-1 in comparative example 4 was changed to HT 2-3.

[ examples 27 to 48]

Examples 27 to 48: the second hole transport layer material of the organic light emitting device was sequentially changed to the compounds 4, 8,11, 22, 29, 79, 99, 110, 157, 187, 227, 234, 266, 280, 296, 308, 319, 347, 368, 440, 451, 505 of the present invention, and the other steps were the same as in comparative example 4.

The driving voltage and the luminous efficiency of the organic light emitting device were tested by combining test software, a computer, a K2400 digital source manufactured by Keithley, usa, and a PR788 spectral scanning luminance meter manufactured by Photo Research, usa, into a combined IVL test system. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 2. Table 2 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.

Table 2 test of light emitting characteristics of light emitting device

Note: t95 denotes a current density of 10mA/cm²In the case where the device luminance decaysTime to 95%;

as can be seen from the results of table 2, the triarylamine compound of the present invention, when applied to an organic light emitting device, particularly as a second hole transport layer material, significantly improved the light emitting efficiency of the organic light emitting device and reduced the driving voltage, compared to comparative examples 4 to 6, and is a good organic light emitting material.

Blue organic light emitting device (cover layer)

Comparative example 7 device preparation example:

comparative example 7: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO-Ag-ITO substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.

On the prepared ITO-Ag-ITO transparent electrode, a hole injection layer m-MTDATA/16nm, a hole transport layer NPB/105nm, a luminescent layer (host H-31: BD (97%: 3% mixed))/23 nm, and an electron transport layer ET-2 are evaporated in a layer-by-layer vacuum evaporation mode: liq₃(1:1)/19nm, an electron injection layer LiF/1nm, a cathode Mg-Ag/19nm, and a vapor plating cover layer CP-1/72nm on the cathode. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:

comparative example 8: the cap material CP-1 of comparative example 7 was changed to CP-2, and an organic light emitting device of comparative example 8 was fabricated in the same manner as in comparative example 7.

[ examples 49 to 62]

Examples 49 to 62: the capping layer material CP-1 of the organic light emitting device was sequentially changed to the compounds 8,11, 38, 99, 110, 217, 227, 266, 288, 296, 301, 308, 319, 505 of the present invention, and the other steps were the same as in comparative example 7.

The test software, computer, K2400 digital source manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic light emitting device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 3. Table 3 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.

Table 3 test of light emitting characteristics of light emitting device

Note: t95 denotes a current density of 10mA/cm²In this case, the time taken for the luminance of the device to decay to 95%;

as can be seen from the results in table 3, the triarylamine compound of the present invention, when applied to an organic light emitting device as a capping layer material, can effectively improve the light extraction efficiency and thus the light emitting efficiency of the organic light emitting device, compared to comparative examples 7 to 8, and is a capping layer material for an organic light emitting device with good performance.

It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.