Triarylamine-based organic compound and organic electroluminescent device

Abstract

The application relates to the field of organic electroluminescent materials, in particular to a triarylamine organic compound and an organic electroluminescent device. The triarylamine organic compound has a chemical structure as shown in formula (1): the triarylamine compound provided by the application has excellent hole transport characteristics and electron blocking characteristics, a relatively high triplet energy level and good molecular stability, is applied to an organic layer of an OLED device, in particular an electron blocking layer, and can effectively improve the light-emitting efficiency and service life of the device.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials, and in particular to a triarylamine organic compound and an organic electroluminescent device. Background Technology

[0002] Electroluminescence (EL) refers to the phenomenon that luminescent materials emit light when excited by electric current and electric field under the influence of an electric field. It is a light-emitting process that directly converts electrical energy into light energy.

[0003] Organic light-emitting diodes (OLEDs) are electronic devices that convert electrical energy into light energy. Compared to traditional liquid crystal displays (LCDs), OLEDs do not require a backlight, are thinner and lighter, and offer advantages such as high brightness, wide viewing angles, low power consumption, and fast response times. Furthermore, they can be fabricated on flexible substrates to create bendable or rollable displays, thus attracting widespread attention from academia and industry.

[0004] Compared to inorganic light-emitting materials, organic electroluminescent materials have the following advantages: good processability, allowing for film formation through various methods such as evaporation, spin coating, or inkjet printing; and easily controllable molecular structure, where altering the chemical structure of the molecules changes their optical and electrical properties to varying degrees, thus meeting the needs of different functional layers in devices. Typically, OLED devices consist of three main parts: an anode, a cathode, and an organic layer between the anode and cathode. The electron-blocking layer, as a functional layer, suppresses reverse current, facilitates hole transport, and blocks high-energy excitons. Selecting a suitable electron-blocking layer material is crucial for effectively improving the luminous efficiency and lifespan of the device. However, currently used electron-blocking layer materials suffer from at least one of the following defects to varying degrees: low hole mobility, poor molecular stability, and poor energy level matching with adjacent light-emitting or functional layers. These factors all limit the improvement of OLED device performance. Therefore, it is necessary to further develop high-performance electron-blocking layer materials. Summary of the Invention

[0005] In view of the shortcomings of the prior art described above, the object of the present invention is to provide a triarylamine organic compound and an organic electroluminescent device containing the same, so as to solve the problems in the prior art.

[0006] To achieve the above and other related objectives, the present invention provides a triarylamine organic compound having a chemical structure as shown in formula (1):

[0007]

[0008] in,

[0009] L0, L1, and L2 may be the same as or different from each other, and are independently selected from single bonds, substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, and substituted or unsubstituted heteroaryl groups with 3 to 20 carbon atoms.

[0010] Ar1 and Ar2 may be the same or different from each other, and are independently selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, or substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms.

[0011] R is selected from one of the following groups, either substituted or unsubstituted:

[0012]

[0013] In any of the above groups, the carbon on any one and only one aromatic ring or heteroaromatic ring is a bonding site;

[0014] R1 to R3 may be the same or different from each other, and are independently selected from deuterium, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or heteroaryl groups having 3 to 20 carbon atoms; m, n, and p are the number of substituent groups R1, R2, and R3, respectively, and are independently selected from 0, 1, 2, 3, or 4.

[0015] Another aspect of the present invention provides an organic electroluminescent material comprising the triarylamine organic compounds described in the present invention.

[0016] Another aspect of the present invention provides organic compounds for use as functional materials in organic electronic devices, including organic electroluminescent devices, organic thin-film transistors, organic solar cells, organic-inorganic hybrid solar cells, optical sensors, radio frequency identification tags, or electronic paper.

[0017] Another aspect of the present invention provides an organic electroluminescent device, comprising a first electrode, a second electrode, and one or more functional layers located between the first electrode and the second electrode, wherein the functional layers contain the triarylamine organic compounds described in the present invention.

[0018] Compared with the prior art, the present invention provides a spirofluorene-based triarylamine compound, which, based on the introduction of an aryl amine group at the 4-position of spirofluorene, further introduces an aryl group at the 1-position. Firstly, spirofluorene can be considered as two fluorene molecule fragments sharing a single sp... 3The carbon-atom-based molecular fragments are simple to synthesize and possess excellent stability. Secondly, the introduction of an arylamine group at the 4-position of the spirofluorene molecule endows it with good hole transport properties while maintaining a high triplet energy level, capable of resisting higher-energy excitons, such as those in green and blue phosphorescence. Furthermore, the introduction of an aryl group at the 1-position of the spirofluorene molecule effectively extends the conjugation of the triarylamine, facilitating hole hopping from one molecule to another. Simultaneously, when the molecule is in an electron-losing state during hole transfer, the extended conjugation contributes to the stability of the positive ion state. Therefore, the molecule exhibits even better hole transport properties and stability.

[0019] In summary, the triarylamine compounds provided by this invention possess excellent hole transport and electron blocking properties, high triplet energy levels, and good molecular stability. When applied to the organic layers of OLED devices, especially the electron blocking layers, they can effectively improve the luminous efficiency and lifespan of the devices. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the organic electroluminescent device in the embodiment.

[0021] In the picture:

[0022] 101 base

[0023] 102 First Electrode

[0024] 103 Hole Injection Layer

[0025] 104 Hole Transport Layer

[0026] 105 Electron Blocking Layer

[0027] 106 Emissive Layer

[0028] 107 Hole-blocking layer

[0029] 108 Electron Transport Layer

[0030] 109 Second Electrode Detailed Implementation

[0031] This disclosure will now be described in detail. However, the following description is intended to explain the invention and is not intended to limit the scope of the invention in any way.

[0032] This disclosure relates to a triarylamine organic compound represented by the above formula (1), an organic electroluminescent material comprising the organic compound, and an organic electroluminescent device comprising the organic electroluminescent material.

[0033] The term "triarylamine organic compound" in this disclosure means a compound that can be used in an organic electroluminescent device and can be included, as needed, in any layer constituting the organic electroluminescent device.

[0034] The term "organic electroluminescent material" in this disclosure refers to a material that can be used in an organic electroluminescent device and may contain at least one compound. If desired, the organic electroluminescent material may be contained in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material may be a hole injection material, a hole transport material, a hole assist material, a light-emitting assist material, an electron blocking material, a light-emitting material (including host material and dopant material), an electron buffer material, a hole blocking material, an electron transport material, or an electron injection material, etc.

[0035] In this disclosure, the term "linear or branched alkyl group having 1 to 10 carbon atoms" refers to a linear or branched alkyl group having 1 to 10 carbon atoms constituting the chain, wherein the number of carbon atoms is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The aforementioned alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, etc.

[0036] In this disclosure, the term "cycloalkyl group having 3 to 10 carbon atoms" refers to a mono- or polycyclic hydrocarbon having 3 to 10 carbon atoms in its cyclic skeleton, wherein the number of carbon atoms is preferably 3 to 9, more preferably 3 to 8, and even more preferably 3 to 7. The aforementioned cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, etc.

[0037] In this disclosure, the term "alkoxy" refers to -O (alkyl). Optionally, the alkyl portion of an alkoxy group may contain 1-10 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms, etc. Alkoxy groups may include, for example, but not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, etc.

[0038] In this disclosure, the term "substituted or unsubstituted (aryl) group having 6 to 40 carbon atoms" refers to a monocyclic or fused-ring group derived from an aromatic hydrocarbon having 6 to 40 cyclic carbon atoms, wherein the number of cyclic carbon atoms is preferably 6 to 30, 6 to 20, more preferably 6 to 15, and may be partially saturated and may contain a spirostructure. Specific examples of aryl groups include phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, binatyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, dimethylfluorenyl, diphenylfluorenyl, benzo[fluorenyl], diphenylbenzo[fluorenyl], dibenzo[fluorenyl], phenanthrene, benzo[phenanthrene], phenylphenanthrene, anthracene, benzo[anthrene], indole, triphenylene, pyrene, tetraphenyl, peryl, benzo[fluorenyl], naphthyl, fluoranthyl, benzo[fluorenyl], tolyl, xylyl, trimethylyl, cumene, spiro[fluorenyl-fluorenyl], spiro[fluorenyl-benzo[fluorenyl]], azulel, tetramethyl-dihydrophenanthrene, etc. More specifically, the aryl group can be o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesitylelel, o-cumenyl, m-cumenyl, p-cumenyl, p-tert-butylphenyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4'-tert-butyl-p-terphenyl-4-yl, o-biphenyl, m-biphenyl, p-biphenyl, o-terphenyl, m-terphenyl-4-yl, m-terphenyl-3- 1-Terphenyl-2-yl, p-Terphenyl-4-yl, p-Terphenyl-3-yl, p-Terphenyl-2-yl, m-Tetraphenyl, 1-Naphthyl, 2-Naphthyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-fluorenyl, 9,9-dimethyl-1-fluorenyl, 9,9-dimethyl-2-fluorenyl, 9,9-dimethyl-3-fluorenyl, 9,9-dimethyl-4-fluorenyl, 9,9-diphenyl-1-fluorenyl, 9,9-diphenyl-2-fluorenyl, 9,9-diphenyl -3-fluorenyl, 9,9-diphenyl-4-fluorenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, 1-yl, 2-yl, 3-yl, 4-yl, 5-yl, 6-yl, benzo[c]phenanthyl, benzo[g]yl, 1-triphenylene, 2-triphenylene, 3-triphenylene, 4-triphenylene, 3-fluoranthyl, 4-fluoranthyl, 8-fluoranthyl, 9-fluoranthyl, benzo[fluoranthyl]fluoranthyl, 11,11-dimethyl-1-phenylene 11,11-dimethyl-2-benzo[a]fluorenyl, 11,11-dimethyl-3-benzo[a]fluorenyl, 11,11-dimethyl-4-benzo[a]fluorenyl, 11,11-dimethyl-5-benzo[a]fluorenyl, 11,11-dimethyl-6-benzo[a]fluorenyl, 11,11-dimethyl-7-benzo[a]fluorenyl, 11,11-dimethyl-8-benzo[a]fluorenyl, 11,11-dimethyl-9-benzo[a]fluorenyl, 11,11-Dimethyl-10-benzo[a]fluorenyl, 11,11-dimethyl-1-benzo[b]fluorenyl, 11,11-dimethyl-2-benzo[b]fluorenyl, 11,11-dimethyl-3-benzo[b]fluorenyl, 11,11-dimethyl-4-benzo[b]fluorenyl, 11,11-dimethyl-5-benzo[b]fluorenyl, 11,11 -dimethyl-6-benzo[b]fluorenyl, 11,11-dimethyl-7-benzo[b]fluorenyl, 11,11-dimethyl-8-benzo[b]fluorenyl, 11,11-dimethyl-9-benzo[b]fluorenyl, 11,11-dimethyl-10-benzo[b]fluorenyl, 11,11-dimethyl-1-benzo[c]fluorenyl, 11,11-di Methyl-2-benzo[c]fluorenyl, 11,11-dimethyl-3-benzo[c]fluorenyl, 11,11-dimethyl-4-benzo[c]fluorenyl, 11,11-dimethyl-5-benzo[c]fluorenyl, 11,11-dimethyl-6-benzo[c]fluorenyl, 11,11-dimethyl-7-benzo[c]fluorenyl, 11,11-dimethyl- 8-Benzo[c]fluorenyl, 11,11-dimethyl-9-benzo[c]fluorenyl, 11,11-dimethyl-10-benzo[c]fluorenyl, 11,11-diphenyl-1-benzo[a]fluorenyl, 11,11-diphenyl-2-benzo[a]fluorenyl, 11,11-diphenyl-3-benzo[a]fluorenyl, 11,11-diphenyl-4- Benzo[a]fluorenyl, 11,11-diphenyl-5-benzo[a]fluorenyl, 11,11-diphenyl-6-benzo[a]fluorenyl, 11,11-diphenyl-7-benzo[a]fluorenyl, 11,11-diphenyl-8-benzo[a]fluorenyl, 11,11-diphenyl-9-benzo[a]fluorenyl, 11,11-diphenyl-10-benzo[a]fluorenyl [a]fluorenyl, 11,11-diphenyl-1-benzo[b]fluorenyl, 11,11-diphenyl-2-benzo[b]fluorenyl, 11,11-diphenyl-3-benzo[b]fluorenyl, 11,11-diphenyl-4-benzo[b]fluorenyl, 11,11-diphenyl-5-benzo[b]fluorenyl, 11,11-diphenyl-6-benzo[b] Fluorenyl, 11,11-diphenyl-7-benzo[b]fluorenyl, 11,11-diphenyl-8-benzo[b]fluorenyl, 11,11-diphenyl-9-benzo[b]fluorenyl, 11,11-diphenyl-10-benzo[b]fluorenyl, 11,11-diphenyl-1-benzo[c]fluorenyl, 11,11-diphenyl-2-benzo[c]fluorenyl 11,11-diphenyl-3-benzo[c]fluorenyl, 11,11-diphenyl-4-benzo[c]fluorenyl, 11,11-diphenyl-5-benzo[c]fluorenyl, 11,11-diphenyl-6-benzo[c]fluorenyl, 11,11-diphenyl-7-benzo[c]fluorenyl, 11,11-diphenyl-8-benzo[c]fluorenyl, 11,11-Diphenyl-9-benzo[c]fluorenyl, 11,11-diphenyl-10-benzo[c]fluorenyl, 9,9,10,10-tetramethyl-9,10-dihydro-1-phenanthyl, 9,9,10,10-tetramethyl-9,10-dihydro-2-phenanthyl, 9,9,10,10-tetramethyl-9,10-dihydro-3-phenanthyl, 9,9,10,10-tetramethyl-9,10-dihydro-4-phenanthyl, etc.

[0039] In this disclosure, the term "substituted or unsubstituted (hybrid)aryl group having 3 to 40 carbon atoms" refers to an aryl group having a ring skeleton atom comprising at least one heteroatom selected from the group consisting of B, N, O, S, Si, P, Se, and Ge, preferably at least one heteroatom selected from N, O, and S, wherein the number of carbon atoms in the ring skeleton is preferably 3 to 30, 2 to 25, or 2 to 20. The number of heteroatoms in the heteroaryl group is preferably 1 to 4. The aforementioned heteroaryl group may be a monocyclic ring or a fused ring condensed with at least one benzene ring; and may be partially saturated. Furthermore, in this document, the aforementioned heteroaryl group may be a heteroaryl group formed by attaching at least one heteroaryl group or aryl group to a heteroaryl group via one or more single bonds. Specific examples of heteroaryl groups can include monocyclic heteroaryl groups, including furanyl, thiophene, pyrrole, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, tetrazolyl, furazonyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and fused-ring heteroaryl groups, including benzofuranyl, benzothiophene, isobenzofuranyl, dibenzofuranyl, dibenzothiophene, dibenzoselenophenyl, benzofuranoquinolinyl, benzofuranoquinazolinyl, benzofuranonaphridyl, benzofuranopyrimidyl, naphthofuranopyrimidyl, benzothiophenequinolinyl, benzothiophenequinazolinyl, benzothiophene naphridyl, benzothiophene Benzpyridyl, naphthothienylpyrimidyl, pyrimidindolyl, benzopyrimidindolyl, benzofuranopyrazinyl, naphthofuranopyrazinyl, benzothiophenepyrazinyl, naphthothiophenepyrazinyl, pyrazinindolyl, benzopyrazinindolyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisooxazolyl, benzooxazolyl, imidazopyridyl, isoindolyl, indolyl, benzoindolyl, indazole, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazole, azacarbazole, benzocarbazole, dibenzocarbazole, phenoxazinyl, phenanthidyl, benzodioxacyclopentenyl, indololinyl, acridineyl, silafluoryl (en yl), germanofluorenyl, benzotriazolyl, phenazinyl, imidazopyridyl, benzopyranoquinazolinyl, thiobenzopyranoquinazolinyl, dimethylbenzopyrimidinyl, indolecarbazoleyl, indenecarbazoleyl, etc. More specifically, heteroaryl groups can be 1-pyrrolithyl, 2-pyrrolithyl, 3-pyrrolithyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl, 1,2,3-triazin-4-yl, 1,2,4-triazin-3-yl, 1,3,5-Triazine-2-yl, 1-Imidazolyl, 2-Imidazolyl, 1-Pyrazolyl, 1-Indolithidyl, 2-Indolithidyl, 3-Indolithidyl, 5-Indolithidyl, 6-Indolithidyl, 7-Indolithidyl, 8-Indolithidyl, 2-Imidazolopyridyl, 3-Imidazolopyridyl, 5-Imidazolopyridyl, 6-Imidazolopyridyl 1-Indolyl, 2-Indolyl, 3-Indolyl, 4-Indolyl, 5-Indolyl, 6-Indolyl, 7-Indolyl, 1-Isoindolyl, 2-Isoindolyl, 3-Isoindolyl, 4-Isoindolyl, 5-Isoindolyl, 6-Isoindolyl, 7-Isoindolyl, 2-Furfuryl, 3-Furfuryl, 2- Benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolinyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl 6-Quinolinyl, 7-Quinolinyl, 8-Quinolinyl, 1-Isoquinolinyl, 3-Isoquinolinyl, 4-Isoquinolinyl, 5-Isoquinolinyl, 6-Isoquinolinyl, 7-Isoquinolinyl, 8-Isoquinolinyl, 2-Quinoxolinyl, 5-Quinoxolinyl, 6-Quinoxolinyl, 1-Carbazoleyl, 2-Carbazoleyl, 3-Carbazoleyl, 4-Carbazoleyl, 9-Carbazoleyl, Azacarbazoleyl-1 -yl, azacarbazole-2-yl, azacarbazole-3-yl, azacarbazole-4-yl, azacarbazole-5-yl, azacarbazole-6-yl, azacarbazole-7-yl, azacarbazole-8-yl, azacarbazole-9-yl, 1-phenanthridyl, 2-phenanthridyl, 3-phenanthridyl, 4-phenanthridyl, 6-phenanthridyl, 7-phenanthridyl, 8-phenanthridyl, 9-phenanthridyl, 1 0-Phenyridyl, 1-Acridinel, 2-Acridinel, 3-Acridinel, 4-Acridinel, 9-Acridinel, 2-Oxazolyl, 4-Oxazolyl, 5-Oxazolyl, 2-Oxadiazolyl, 5-Oxadiazolyl, 3-Furazonyl, 2-Thienyl, 3-Thienyl, 2-Methylpyrrole-1-yl, 2-Methylpyrrole-3-yl, 2-Methylpyrrole-4-yl, 2-Methylpyrrole -5-yl, 3-methylpyrrolo-1-yl, 3-methylpyrrolo-2-yl, 3-methylpyrrolo-4-yl, 3-methylpyrrolo-5-yl, 2-tert-butylpyrrolo-4-yl, 3-(2-phenylpropyl)pyrrolo-1-yl, 2-methyl-1-indolyl, 4-methyl-1-indolyl, 2-methyl-3-indolyl, 4-methyl-3-indolyl, 2-tert-butyl-1-indolyl, 4-tert-butyl-1-indolyl, 2-tert-butyl-3-indolyl, 4-tert-butyl-3-indolyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl, 1-dibenzothiophene, 2-dibenzothiophene, 3-dibenzothiophene, 4-dibenzothiophene, 1-naphtho-[1,2-[b]-benzofuranyl, 2-naphtho-[1,2-b]-benzofuranyl, 3-naphtho-[1,2-b]-benzofuranyl, 4-naphtho-[1,2-b]-benzofuranyl, 5-naphtho-[1,2-b]-benzofuranyl, 6-naphtho-[1,2-b]-benzofuranyl, 7-naphtho-[1,2-b]-benzofuranyl 8-Naphtho-[1,2-b]-benzofuranyl, 9-Naphtho-[1,2-b]-benzofuranyl, 10-Naphtho-[1,2-b]-benzofuranyl, 1-Naphtho-[2,3-b]-benzofuranyl, 2-Naphtho-[2,3-b]-benzofuranyl, 3-Naphtho-[2,3-b]-benzofuranyl, 4-Naphtho-[2, [3-b]-benzofuranyl, 5-naphtho-[2,3-b]-benzofuranyl, 6-naphtho-[2,3-b]-benzofuranyl, 7-naphtho-[2,3-b]-benzofuranyl, 8-naphtho-[2,3-b]-benzofuranyl, 9-naphtho-[2,3-b]-benzofuranyl, 10-naphtho-[2,3-b]-benzofuranyl 1-Naphtho-[2,1-b]-benzofuranyl, 2-Naphtho-[2,1-b]-benzofuranyl, 3-Naphtho-[2,1-b]-benzofuranyl, 4-Naphtho-[2,1-b]-benzofuranyl, 5-Naphtho-[2,1-b]-benzofuranyl, 6-Naphtho-[2,1-b]-benzofuranyl, 7-Naphtho-[2, 1-b]-benzofuranyl, 8-naphtho-[2,1-b]-benzofuranyl, 9-naphtho-[2,1-b]-benzofuranyl, 10-naphtho-[2,1-b]-benzofuranyl, 1-naphtho-[1,2-b]-benzothiophenyl, 2-naphtho-[1,2-b]-benzothiophenyl, 3-naphtho-[1,2-b]-benzothiophene 4-Naphtho-[1,2-b]-benzothiophene, 5-Naphtho-[1,2-b]-benzothiophene, 6-Naphtho-[1,2-b]-benzothiophene, 7-Naphtho-[1,2-b]-benzothiophene, 8-Naphtho-[1,2-b]-benzothiophene, 9-Naphtho-[1,2-b]-benzothiophene, 10-Naphtho-[1 [2,3-b]-benzothiophene, 1-naphtho-[2,3-b]-benzothiophene, 2-naphtho-[2,3-b]-benzothiophene, 3-naphtho-[2,3-b]-benzothiophene, 4-naphtho-[2,3-b]-benzothiophene, 5-naphtho-[2,3-b]-benzothiophene, 1-naphtho-[2,1-b]-benzothiophene 2-Naphtho-[2,1-b]-benzothiophene, 3-Naphtho-[2,1-b]-benzothiophene, 4-Naphtho-[2,1-b]-benzothiophene, 5-Naphtho-[2,1-b]-benzothiophene, 6-Naphtho-[2,1-b]-benzothiophene, 7-Naphtho-[2,1-b]-benzothiophene, 8-Naphtho-[2,1-b]-benzothiophene1-b]-benzothiophene, 9-naphtho-[2,1-b]-benzothiophene, 10-naphtho-[2,1-b]-benzothiophene, 2-benzofurano[3,2-d]pyrimidinyl, 6-benzofurano[3,2-d]pyrimidinyl, 7-benzofurano[3,2-d]pyrimidinyl, 8-benzofurano[3,2-d]pyrimidinyl, 9-benzofurano[3,2-d]pyrimidinyl, 2-benzothio[3,2-d]pyrimidinyl, 6-benzothio[3,2-d]pyrimidinyl, 7-benzothio[3,2-d]pyrimidinyl, 8-benzothio[3,2-d]pyrimidinyl, 9-benzothio[3,2-d]pyrimidinyl, 2-benzofurano[3,2-d]pyrazinyl 6-Benzofurano[3,2-d]pyrazinyl, 7-Benzofurano[3,2-d]pyrazinyl, 8-Benzofurano[3,2-d]pyrazinyl, 9-Benzofurano[3,2-d]pyrazinyl, 2-Benzothio[3,2-d]pyrazinyl, 6-Benzothio[3,2-d]pyrazinyl, 7-Benzothio[3,2-d]pyrazinyl Phthalinyl, 8-benzothio[3,2-d]pyrazinyl, 9-benzothio[3,2-d]pyrazinyl, 1-silylfluorenyl, 2-silylfluorenyl, 3-silylfluorenyl, 4-silylfluorenyl, 1-germaniumfluorenyl, 2-germaniumfluorenyl, 3-germaniumfluorenyl, 4-germaniumfluorenyl, 1-dibenzo[2,3-]selenophenyl, 2-dibenzo[2,3-]selenophenyl, 3-dibenzo[2,3-]selenophenyl, 4-dibenzo[2,3-]selenophenyl, etc.

[0040] Furthermore, the term "substituted" in the expression "substituted or unsubstituted" means that a hydrogen atom in a functional group is replaced by another atom or functional group (i.e., a substituent). Examples of substituents include deuterium, cyano, a straight-chain or branched alkyl group with 1 to 10 substituted or unsubstituted carbon atoms, a cycloalkyl group with 3 to 10 substituted or unsubstituted carbon atoms, an alkoxy group with 1 to 10 substituted or unsubstituted carbon atoms, an aryl group with 6 to 20 substituted or unsubstituted carbon atoms, and a heteroaryl group with 3 to 20 substituted or unsubstituted carbon atoms. Preferably, the substituents are deuterium, cyano, a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a deuterated alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 20 carbon atoms, methylphenyl, tert-butylphenyl, and a heteroaryl group with 3 to 20 carbon atoms.

[0041] The triarylamine organic compounds according to the present invention will be described below.

[0042] The triarylamine organic compounds have the chemical structure shown in formula (1):

[0043]

[0044] in,

[0045] L0, L1, and L2 may be the same as or different from each other, and are independently selected from single bonds, substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, and substituted or unsubstituted heteroaryl groups with 3 to 20 carbon atoms.

[0046] Ar1 and Ar2 may be the same or different from each other, and are independently selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, or substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms.

[0047] R is selected from one of the following groups, either substituted or unsubstituted:

[0048]

[0049] In any of the above groups, the carbon on any one and only one aromatic ring or heteroaromatic ring is a bonding site;

[0050] R1 to R3 may be the same or different from each other, and are independently selected from deuterium, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or heteroaryl groups having 3 to 20 carbon atoms; m, n, and p are the number of substituent groups R1, R2, and R3, respectively, and are independently selected from 0, 1, 2, 3, or 4.

[0051] In this application, in L0, L1, L2, Ar1, Ar2, and R1-R3, the substituent in "substitution" is selected from deuterium, cyano, substituted or unsubstituted straight-chain or branched alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, aryl groups with 6 to 20 carbon atoms, and heteroaryl groups with 3 to 20 carbon atoms. Preferably, the substituent in "substitution" is selected from deuterium, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated alkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, phenyl, methylphenyl, tert-butylphenyl, naphthyl, biphenyl, etc.

[0052] In this application, any hydrogen atom in R can be replaced by one of deuterium, an alkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, phenyl, methylphenyl, or tert-butylphenyl. Preferably, any hydrogen atom in R can be replaced by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated sec-butyl, phenyl, methylphenyl, or tert-butylphenyl.

[0053] In some embodiments, R is selected from substituted or unsubstituted phenyl groups, where “substituted” means that any hydrogen atom on the group can be substituted by one of deuterium, an alkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, phenyl, methylphenyl, or tert-butylphenyl. Optionally, any hydrogen atom in the phenyl group can be substituted by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated sec-butyl, phenyl, methylphenyl, or tert-butylphenyl.

[0054] In some embodiments, R is selected from substituted or unsubstituted fluorenyl groups, where "substituted" means that any hydrogen atom on the group can be substituted by one of deuterium, an alkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, phenyl, methylphenyl, or tert-butylphenyl. Optionally, any hydrogen atom in the fluorenyl group can be substituted by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated sec-butyl, phenyl, methylphenyl, or tert-butylphenyl.

[0055] In some embodiments, R is selected from substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran, or substituted or unsubstituted dibenzoselenyl; the term "substituted" means that any hydrogen atom on the group can be substituted by one of deuterium, an alkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, phenyl, methylphenyl, or tert-butylphenyl. Optionally, any hydrogen atom of dibenzothiophene, dibenzofuran, or dibenzoselenyl can be substituted by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated sec-butyl, phenyl, methylphenyl, or tert-butylphenyl.

[0056] In some embodiments, L0, L1, and L2 may be the same as or different from each other, and are independently selected from single bonds, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms. Optionally, L0, L1, and L2 may be the same as or different from each other, and are independently selected from single bonds, substituted or unsubstituted aryl groups having 6 to 15 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 15 carbon atoms. Optionally, L0, L1, and L2 may be the same as or different from each other, and are independently selected from single bonds, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 10 carbon atoms. Preferably, L0, L1, and L2 may be the same as or different from each other, and are each independently selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophene. The carbon atoms on any two and only two of the aromatic or heteroaromatic rings in L0, L1, and L2 are bonding sites. The aforementioned "substitution" means that any hydrogen atom in the group can be replaced by one of deuterium, an alkyl group with 1 to 4 carbon atoms, a deuterated alkyl group with 1 to 4 carbon atoms, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl, methylphenyl, or tert-butylphenyl. Optionally, the aforementioned "substitution" means that any hydrogen atom in the group can be replaced by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated sec-butyl, phenyl, methylphenyl, or tert-butylphenyl.

[0057] In some embodiments, Ar1 and Ar2 may be the same as or different from each other, and are independently selected from substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, or substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms. Optionally, Ar1 and Ar2 may be the same as or different from each other, and are independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms. Optionally, Ar1 and Ar2 may be the same as or different from each other, and are independently selected from substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaryl groups having 3 to 20 carbon atoms. Optionally, Ar1 and Ar2 may be the same as or different from each other, and are independently selected from one of the following substituted or unsubstituted groups:

[0058]

[0059] In any of the aforementioned groups, a carbon atom on one and only one aromatic or heteroaromatic ring is a bonding site, and / or any hydrogen atom may be substituted by one of deuterium, an alkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl, methylphenyl, or tert-butylphenyl. Optionally, any hydrogen atom may be substituted by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated sec-butyl, phenyl, methylphenyl, or tert-butylphenyl.

[0060] In some embodiments, R1 to R3 may be the same as or different from each other, and are independently selected from deuterium, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or heteroaryl groups having 3 to 20 carbon atoms. Optionally, R1 to R3 may be the same as or different from each other, and are independently selected from deuterium, straight-chain or branched alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, or heteroaryl groups having 3 to 10 carbon atoms. In specific embodiments, R1 to R3 may be the same as or different from each other, and are independently selected from deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated sec-butyl, phenyl, deuterated phenyl, etc.

[0061] In some embodiments, m, n, and p represent the number of substituent groups R1, R2, and R3, respectively, each independently selected from 0, 1, 2, 3, or 4.

[0062] According to some embodiments, the triarylamine organic compounds are selected from any of the following chemical structures (when R is selected from substituted or unsubstituted phenyl):

[0063]

[0064]

[0065]

[0066]

[0067] According to some embodiments, the triarylamine organic compounds are selected from any of the following chemical structures (R is selected from substituted or unsubstituted fluorene groups):

[0068]

[0069] According to some embodiments, the triarylamine organic compound is selected from any of the following chemical structures: (R is selected from substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran, or substituted or unsubstituted dibenzoselenyl)

[0070]

[0071]

[0072]

[0073] In the following text, an organic electroluminescent device that applies the above-described organic electroluminescent compound and / or the above-described organic electroluminescent material will be described.

[0074] An organic electroluminescent device according to one embodiment includes a first electrode; a second electrode; and at least one organic layer inserted between the first electrode and the second electrode. The organic layer may comprise at least one layer selected from the group consisting of a hole transport layer, a hole injection layer, an electron blocking layer, a hole auxiliary layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, an electron injection layer, an intermediate layer, a hole blocking layer, and an electron auxiliary layer, and each layer may further consist of several layers.

[0075] The aromatic amine organic compound represented by formula (1) in this disclosure may be contained in one or more layers constituting an organic electroluminescent device. According to one embodiment, the organic layer includes a hole transport region and / or an electron transport region and / or a light-emitting layer containing the organic electroluminescent compound according to the invention, for example, a hole transport layer and / or a hole assist layer and / or a hole blocking layer and / or an electron assist layer and / or a light-emitting layer.

[0076] One of the first electrode and the second electrode can be an anode, and the other can be a cathode. The first electrode and the second electrode can each be formed of a transmissive conductive material, a semi-transmissive reflective conductive material, or a reflective conductive material. Depending on the types of materials forming the first electrode and the second electrode, the organic electroluminescent device can be a top-emitting type, a bottom-emitting type, or a side-emitting type.

[0077] A hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof can be used between the anode and the emissive layer. The hole injection layer can be multilayered to reduce the hole injection barrier (or hole injection voltage) from the anode to the hole transport layer or electron blocking layer, wherein each of the multilayers can use two compounds simultaneously. The hole injection layer can be doped with a p-type dopant. Furthermore, an electron blocking layer can be placed between the hole transport layer (or hole injection layer) and the emissive layer, and can confine excitons within the emissive layer by blocking electrons from escaping from the emissive layer to prevent light leakage. The hole transport layer or electron blocking layer can be multilayered, and each layer can use multiple compounds.

[0078] An electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof can be used between the light-emitting layer and the cathode. The electron buffer layer can be multilayered to control electron injection and improve the interface properties between the light-emitting layer and the electron injection layer, wherein each of the multilayers can use two compounds simultaneously. The hole blocking layer or electron transport layer can also be multilayered, wherein each of the multilayers can use multiple compounds. Furthermore, the electron injection layer can be doped with an n-type dopant.

[0079] An auxiliary light-emitting layer can be placed between the anode and the light-emitting layer, or between the cathode and the light-emitting layer. When placed between the anode and the light-emitting layer, it can promote hole injection and / or hole transport, or prevent electron overflow. When placed between the cathode and the light-emitting layer, it can promote electron injection and / or electron transport, or prevent hole overflow. Furthermore, a hole auxiliary layer can be placed between the hole transport layer (or hole injection layer) and the light-emitting layer, and can effectively promote or limit the hole transport rate (or hole injection rate), thereby enabling charge balance control. When an organic electroluminescent device includes two or more hole transport layers, the further included hole transport layers can serve as hole auxiliary layers or electron blocking layers. The auxiliary light-emitting layer, hole auxiliary layer, or electron blocking layer can improve the efficiency and / or lifetime of the organic electroluminescent device.

[0080] In the organic electroluminescent device disclosed herein, it is preferable to place at least one layer (hereinafter referred to as "surface layer") selected from chalcogenide layers, metal halide layers, and metal oxide layers on one or more inner surfaces of one or two electrodes. Specifically, it is preferable to place silicon and aluminum chalcogenide (including oxide) layers on the anode surface of the electroluminescent dielectric layer, and it is preferable to place the metal halide layer or metal oxide layer on the cathode surface of the electroluminescent dielectric layer. The operational stability of the organic electroluminescent device can be obtained through the surface layer. Preferably, the chalcogenides include SiOX (1≤X≤2), AlOX (1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, rare earth metal fluorides, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.

[0081] Furthermore, in the organic electroluminescent device of this disclosure, it is preferable to place a mixed region of electron transport compound and reducing dopant, or a mixed region of hole transport compound and oxidizing dopant, on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to anion, and thus it becomes easier to inject and transport electrons from the mixed region into the electroluminescent medium. Similarly, the hole transport compound is oxidized to cation, and thus it becomes easier to inject and transport holes from the mixed region into the electroluminescent medium. Preferably, the oxidizing dopant includes various Lewis acids and acceptor compounds, and the reducing dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. The reducing dopant layer can be used as a charge-generating layer to prepare an organic electroluminescent device having two or more light-emitting layers and emitting white light.

[0082] To form each layer of the organic electroluminescent device of this disclosure, dry film-forming methods such as vacuum evaporation, sputtering, plasma, ion plating, etc., or wet film-forming methods such as inkjet printing, nozzle printing, slot coating, spin coating, dip coating, flow coating, etc., can be used.

[0083] When using a wet film-forming method, a thin film can be formed by dissolving or diffusing the material forming each layer into any suitable solvent (such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.). The solvent can be any solvent in which the material forming each layer can dissolve or diffuse and in which there are no problems with film-forming ability.

[0084] When a layer is formed using an organic electroluminescent compound according to one embodiment, the layer can be formed by the methods listed above, and typically by co-deposition or hybrid deposition. Co-deposition is a hybrid deposition method in which two or more materials are placed in respective individual crucible sources and current is simultaneously applied to two chambers to cause the materials to evaporate and to be co-deposited; and hybrid deposition is a hybrid deposition method in which two or more materials are mixed in a crucible source before being deposited and then current is applied to a chamber to cause the materials to evaporate.

[0085] According to one embodiment, the organic electroluminescent device disclosed herein can be used to manufacture display devices such as smartphones, tablets, laptops, PCs, TVs, or display devices for vehicles, or lighting devices such as outdoor or indoor lighting.

[0086] In the following, the preparation methods of the compounds according to this disclosure will be explained with reference to representative compounds or intermediate compounds in order to provide a detailed understanding of this disclosure.

[0087] Synthesis Example:

[0088] The specific preparation method of the above-mentioned new compounds of the present invention will be described in detail below using multiple synthetic examples. However, the preparation method of the present invention is not limited to these multiple synthetic examples. Those skilled in the art can make any modifications, equivalent substitutions, improvements, etc. on the basis of these examples without departing from the principles of the present invention, and extend the method to the scope of the technical solution claimed in the claims of the present invention.

[0089] Unless otherwise specified, all compounds for which synthesis methods are not mentioned in this invention are commercially available products; mass spectrometry in this invention was performed using a ZABHS mass spectrometer (manufactured by Micromass, UK), and nuclear magnetic resonance was performed using a Bruker 400MHz nuclear magnetic resonance spectrometer (manufactured by Bruker, Germany).

[0090] The compounds involved in this invention can be prepared via the following general synthetic route, but are not limited thereto. Those skilled in the art can make any modifications, equivalent substitutions, improvements, etc., based on this method without departing from the principles of this invention, thereby extending the scope of the technical solutions claimed in this invention.

[0091] Synthesis of compound H1-17:

[0092]

[0093] Synthesis of compound M3

[0094] Under a nitrogen atmosphere, 2-(methoxycarbonyl)phenylboronic acid (compound M1, 7.2 g, 40.0 mmol, 1 eq), 4-bromo-1-chloro-2-iodobenzene (compound M2, 12.7 g, 40.0 mmol, 1 eq), tetra(triphenylphosphine)palladium (462.2 mg, 0.8 mmol, 2% eq), and degassed tetrahydrofuran (100 mL) were added sequentially to a three-necked flask. The mixture was thoroughly mixed, followed by the addition of potassium carbonate (50.0 mL, 2M deionized water, 100.0 mmol, 2.5 eq). The mixture was stirred and refluxed under a nitrogen atmosphere for 6 hours. Thin-layer chromatography analysis showed that there was essentially no reactant residue. The reaction mixture was cooled to room temperature, and ethyl acetate (150 mL) was added. After standing, the mixture separated into layers. The organic phase was collected, and the aqueous phase was extracted with ethyl acetate (3 x 50 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was separated by rapid silica gel column chromatography (mobile phase was a mixture of n-hexane and ethyl acetate) to obtain compound M3 (10.5 g, yield 80.6%).

[0095] Synthesis of compound M4

[0096] Compound M3 (9.8 g, 30.0 mmol, 1 eq) and tetrahydrofuran (100 mL) were added sequentially to a three-necked flask and mixed thoroughly. While stirring, sodium hydroxide (60.0 mL, 1 M deionized water, 60.0 mmol, 2 eq) was slowly added, and the mixture was gradually heated to reflux for 10 hours. Thin-layer chromatography analysis showed that virtually no reactants remained. The reaction system was cooled to room temperature. 2 M hydrochloric acid was added dropwise to adjust the pH to 1–2, during which a large amount of white precipitate was observed to form. The precipitate was filtered, and the filter cake was collected. The filter cake was washed sequentially with sodium carbonate aqueous solution and deionized water, and then dried. The filter cake was placed in a three-necked flask, and dichloromethane (120 mL) was added to dissolve it. The resulting solution was cooled to 0°C, and polyphosphoric acid (PPA, 40.0 g) was slowly added while stirring vigorously. After the addition was complete, stirring was continued, and the reaction system was slowly restored to room temperature and allowed to react for another 10 hours at room temperature. Thin-layer chromatography analysis showed virtually no residue of raw material, so stirring was stopped. The resulting mixture was poured into a large volume of ice water, stirred for 5 minutes, and allowed to stand to separate into layers. The organic phase was collected using a separatory funnel. The organic phase was washed successively with aqueous sodium carbonate solution and saturated saline solution, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was separated by rapid silica gel column chromatography (mobile phase: n-hexane / ethyl acetate mixed solvent) to give compound M4 (6.6 g, yield 74.9%). 1 H NMR (400MHz, DMSO-d6) δ8.00–7.96(m,1H),7.85–7.80(m,1H),7.74(d,J=7.5Hz,1H ),7.65(td,J=7.5,1.5Hz,1H),7.54(d,J=7.6Hz,1H),7.41(td,J=7.5,1.5Hz,1H).

[0097] Synthesis of compound M6

[0098] Under a nitrogen atmosphere, 2-bromobiphenyl (compound M5, 4.7 g, 20.0 mmol, 1 eq) and anhydrous degassed tetrahydrofuran (40 mL) were added sequentially to a dry three-necked flask. Stirring was initiated to allow the solids to dissolve completely. The solution was then cooled to -78°C. While stirring, n-butyllithium (9.6 mL, 2.5 M n-hexane solution, 24.0 mmol, 1.2 eq) was added dropwise to the mixture. After the addition was complete, the reaction mixture was stirred at -78°C for 30 minutes. Subsequently, anhydrous tetrahydrofuran (10 mL) of compound M6 (5.9 g, 20.0 mmol, 1 eq) was added dropwise. After the addition was complete, the reaction mixture was gradually brought to room temperature and stirred for 1 hour. Thin-layer chromatography analysis showed that virtually no reactants remained, at which point stirring was stopped. Deionized water (100 mL) and ethyl acetate (120 mL) were added sequentially to the resulting mixture. After stirring for 5 minutes, the mixture was allowed to stand and separate into layers. The organic phase was collected using a separatory funnel, and the aqueous phase was extracted with ethyl acetate (3 x 30 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was then separated by rapid silica gel column chromatography (using a hexane / ethyl acetate mixture as the mobile phase) to give compound M6 (7.8 g, yield 86.7%).

[0099] Synthesis of compound M7

[0100] Compound M6 (7.2 g, 16.0 mmol, 1 eq), glacial acetic acid (60 mL), and concentrated hydrochloric acid (12 M aqueous solution, 10 mL) were added sequentially to a three-necked flask. After thorough mixing, the reaction system was heated to 80 °C and stirred for hours. Thin-layer chromatography analysis showed that there was essentially no reactant remaining. Stirring was stopped, and the reaction system was cooled to room temperature. The resulting mixture was slowly added to a saturated sodium bicarbonate aqueous solution, followed by dichloromethane (100 mL). After stirring for 5 minutes, the mixture was allowed to stand and separate into layers. The organic phase was collected using a separatory funnel, and the aqueous phase was extracted with dichloromethane (3 x 30 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was then subjected to rapid silica gel column chromatography (mobile phase: hexane / dichloromethane mixed solvent) and recrystallization (hexane / ethanol mixed solvent) to obtain compound M7 (6.2 g, yield 90.2%). Mass spectrometry (m / z) = 429.00 [M+H] + . 1 H NMR (400MHz, DMSO-d6) δ7.86–7.83(m,2H),7.83–7.80(m,1H),7.52(d,J=7.5Hz,1H), 7.46–7.41(m,2H),7.36–7.28(m,5H),7.25(dd,J=7.4,1.6Hz,1H),7.21–7.18(m,2H).

[0101] Synthesis of compound M1-17

[0102] Under a nitrogen atmosphere, phenylboronic acid (compound i1-17, 2.7 g, 22.0 mmol, 1.1 eq), compound M7 (8.6 g, 20.0 mmol, 1 eq), tetrakis(triphenylphosphine)palladium (231 mg, 0.4 mmol, 2% eq), and degassed toluene (80 mL) were added sequentially to a three-necked flask. The mixture was thoroughly stirred, followed by the addition of potassium carbonate (25.0 mL, 2M deionized water, 50.0 mmol, 2.5 eq) and degassed ethanol (40 mL). The mixture was stirred and refluxed under a nitrogen atmosphere for 8 hours. Thin-layer chromatography analysis showed that there was essentially no reactant remaining. The reaction mixture was cooled to room temperature, and dichloromethane (50 mL) was added. After standing, the mixture separated into layers. The organic phase was collected, and the aqueous phase was extracted with dichloromethane (3 x 30 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was subjected to rapid silica gel column chromatography (mobile phase: hexane / dichloromethane mixed solvent) and recrystallization (hexane / ethanol mixed solvent) to obtain compound M1-17 (7.0 g, yield 82.0%).

[0103] Synthesis of compound H1-17

[0104] Under a nitrogen atmosphere, compound M1-17 (6.4 g, 15.0 mmol, 1 eq), bis(9,9-dimethylfluorene)amine (compound M1-17, 6.0 g, 15.0 mmol, 1 eq), and degassed anhydrous toluene (60 mL) were added sequentially to a dry three-necked flask. After thorough mixing, sodium tert-butoxide (2.2 g, 22.5 mmol, 1.5 eq), bis(dibenzylacetone)palladium (86.2 mg, 0.15 mmol, 1% eq), and tri-tert-butylphosphine (0.75 mL, 10% n-hexane solution, 0.3 mmol, 2% eq) were added. The mixture was stirred to thoroughly mix the reaction system, and the temperature was raised to reflux under a nitrogen atmosphere. After 9 hours of reaction, thin-layer chromatography analysis showed that there was essentially no reactant remaining, and heating was stopped. After the reaction system cooled to room temperature, a mixture of 5 mL concentrated hydrochloric acid (37% aqueous solution) and 100 mL deionized water was added. The mixture was allowed to stand and separate into layers using a separatory funnel. The organic phase was retained, and the aqueous phase was extracted with toluene (3 × 20 mL). This aqueous phase was combined with the retained organic phase, and the solvent was removed by vacuum distillation. The crude product was then subjected to silica gel column chromatography (using a hexane / toluene mixture as the mobile phase) and recrystallized from a toluene / ethanol mixture to obtain the target compound H1-17 (9.5 g, yield 80.0%). Using compound M7 as the starting material, the overall yield of the two-step reaction was 65.6%. Mass spectrometry (m / z) = 792.36 [M+H] + .1 H NMR(400MHz, DMSO-d6)δ7.84(dd,J=7.2,1.7Hz,2H),7.74–7.71(m,3H),7.70(d,J=7.6Hz,2H),7.60–7.55(m,3H),7.5 0–7.44(m,4H),7.42–7.26(m,12H),7.23(dd,J=7.5,1.5Hz,2H),7.21–7.18(m,3H),6.98–6.95(m,2H),1.59(s,12H).

[0105] Following the preparation method for compounds H1-17, the compounds listed in Table 1 were synthesized. For each compound Hx, the starting materials or intermediate compounds M5, i1-17, ii1-17 involved in the above preparation method are represented as M5-x, ix, ii-x, respectively. The main starting materials used, the intermediates synthesized, the yields, and the mass spectrometry characterization data are shown in Table 1.

[0106] Table 1

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] Synthesis of compound H1-41

[0113]

[0114] Following the preparation method of compound M1-17, compound H1-41 was finally obtained via a two-step Suzuki coupling reaction, passing through intermediate compound M1-41. The preparation of compound H1-41 was carried out according to the method described in application publication number CN 110526825 A. The overall yield of the two-step reaction was 62.4%. Mass spectrometry (m / z) = 882.40 [M+H] + . 1H NMR (400MHz, DMSO-d6) δ7.86–7.83(m,2H),7.74–7.70(m,3H),7.69(d,J=7.5Hz,2H),7.65(d,J=7 .5Hz,1H),7.61–7.56(m,3H),7.48–7.17(m,23H),6.97–6.95(m,2H),2.38(s,3H),1.59(s,12H).

[0115] Following the preparation method for compounds H1-41, the compounds listed in Table 2 were synthesized. For each compound Hx, the starting materials or intermediate compounds M5, i1-41, ii1-41 involved in the above preparation method are represented as M5-x, ix, ii-x, respectively. The main starting materials used, the intermediates synthesized, the yields, and the mass spectrometry characterization data are shown in Table 2.

[0116] Table 2

[0117]

[0118]

[0119]

[0120] The NMR data of representative compounds involved in the synthesis examples are shown in Table 3.

[0121] Table 3

[0122]

[0123]

[0124] Device Examples:

[0125] All compounds used in the device have been purified by sublimation, and their purity is greater than 99.98%.

[0126] The compounds involved in this invention can be used as electron blocking layer materials for various color OLED devices, especially for green OLED devices. Specific device fabrication methods and test results are given below.

[0127] Example 1 of green light device:

[0128] According to such Figure 1The structure shown is used to fabricate a green bottom-emitting organic electroluminescent device. The fabrication process is as follows: A transparent ITO film (150 nm thick) is formed on a glass substrate 101 by magnetron sputtering to obtain a first electrode 102 as the anode. A mixture of compound 1 and compound 2 is deposited on the anode surface as a hole injection layer 103, with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm. Subsequently, compound 2 (100 nm thick) and compound H1-9 (40 nm thick) of the present invention are sequentially deposited on the surface of the hole injection layer to obtain a hole transport layer 104 and an electron blocking layer 105, respectively. Next, compounds 3A, 3B, and 4 are co-deposited on the surface of the electron blocking layer 105 in a mass ratio of 45:45:10 to form an organic light-emitting layer 106 (40 nm thick). Subsequently, compound 5 is sequentially vapor-deposited onto the surface of the organic light-emitting layer to form a hole-blocking layer 107 (10 nm thick), and a mixture of compound 6 and LiQ in a 4:6 mass ratio is deposited to form an electron transport layer 108 (30 nm thick). Finally, magnesium (Mg) and silver (Ag) are mixed and deposited on the surface of the electron transport layer 108 at a vapor deposition rate of 1:9 to form a second electrode 109 with a thickness of 10 nm as a cathode, thus completing the fabrication of the organic light-emitting device.

[0129] The chemical structures of compounds 1–6 and LiQ are shown in Table 4.

[0130] Table 4

[0131]

[0132]

[0133] Examples of green light devices 2-36

[0134] Except for replacing compounds H1-9 with the compounds listed in Table 5 below when forming the electron blocking layer, the organic electroluminescent device was fabricated using the same method as in Example 1 of the green light device.

[0135] Comparative Examples 1-4

[0136] Except that compounds H1-9 were replaced with compounds C1-C4 (chemical structures shown below) when forming the electron blocking layer, the organic electroluminescent device was fabricated using the same method as in Example 1 of the green light device.

[0137]

[0138] The operating voltage and efficiency of the organic electroluminescent device prepared above were calculated using a computer-controlled Keithley 2400 testing system (test current 20 mA / cm²). 2Device lifetime under dark conditions was obtained using a Polaronix (McScience Co.) lifetime measurement system equipped with a power supply and photodiode as detection units (test conditions: constant current 20mA / cm). 2 LT95 refers to the time required for the brightness to decrease from its initial value to 95%. The test results are shown in Table 5.

[0139] Table 5

[0140]

[0141]

[0142] Referring to Table 5, the green light devices 1-36, which use the compounds of the present invention as electron blocking layer materials for organic electroluminescent green light devices, show that, compared with Comparative Examples 1-4, the device voltage is reduced by at least 6.4%, the device efficiency is increased by at least 8.0%, and the lifetime is increased by at least 20.0%.

[0143] Compared to comparative compound C1, the compounds of this invention introduce an aryl group at the para-position of the benzene ring linking the spirofluorene to the arylamine group, extending the effective conjugation length of the molecule and making hole transport more favorable. Therefore, the devices of the embodiments exhibit higher efficiency and lower voltage compared to comparative device 1. On the other hand, the devices of the embodiments have a longer lifetime compared to comparative devices 2 to 4. This may be because spirofluorene has a stable rigid spirocyclic structure, exhibiting stronger molecular stability compared to diphenylfluorene or dimethylfluorene in comparative compounds C2 to C4, and is less susceptible to disruption by excitons in the light-emitting layer.

[0144] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the technical scope disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A triarylamine organic compound having a chemical structure as shown in formula (1): in, L0, L1, and L2 may be the same as or different from each other, and are independently selected from single bonds, substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, and substituted or unsubstituted heteroaryl groups with 3 to 20 carbon atoms. Ar1 and Ar2 may be the same as or different from each other, and each is independently selected from one of the following groups, whether substituted or unsubstituted: In any of the above groups, a carbon atom on any one and only one aromatic ring or heteroaromatic ring is a bonding site, and / or any hydrogen atom can be replaced by one of deuterium, alkyl with 1 to 4 carbon atoms, deuterated alkyl with 1 to 4 carbon atoms, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl, methylphenyl, or tert-butylphenyl. R is selected from one of the following groups, either substituted or unsubstituted: When R is substituted, any hydrogen atom in R is replaced by one of deuterium, methyl, tert-butyl, deuterated methyl, or phenyl. R1 to R3 may be the same or different from each other, and are independently selected from deuterium, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, or heteroaryl groups having 3 to 20 carbon atoms; m, n, and p are the number of substituent groups R1, R2, and R3, respectively, and are independently selected from 0, 1, 2, 3, or 4.

2. The triarylamine organic compound according to claim 1, characterized in that, In L0, L1, L2, Ar1, Ar2, R1 to R3, the substituent in "substitution" is selected from deuterium, cyano, substituted or unsubstituted straight-chain or branched alkyl with 1 to 10 carbon atoms, cycloalkyl with 3 to 10 carbon atoms, alkoxy with 1 to 10 carbon atoms, aryl with 6 to 20 carbon atoms, and heteroaryl with 3 to 20 carbon atoms.

3. The triarylamine organic compound according to claim 1, characterized in that, R is selected from substituted or unsubstituted phenyl groups, where "substituted" means that any hydrogen atom on the group can be replaced by one of deuterium, methyl, tert-butyl, or deuterated methyl.

4. The triarylamine organic compound according to claim 1, characterized in that, R is selected from phenyl.

5. The triarylamine organic compound according to claim 1, characterized in that, R is selected from substituted or unsubstituted fluorenyl groups, where "substituted" means that any hydrogen atom on the group can be replaced by one of deuterium, methyl, tert-butyl, or deuterated methyl.

6. The triarylamine organic compound according to claim 1, characterized in that, R is selected from substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran, or substituted or unsubstituted dibenzoselenyl; the term "substituted" means that any hydrogen atom on the group can be substituted by one of deuterium, methyl, tert-butyl, or deuterated methyl.

7. The triarylamine organic compound according to any one of claims 1 to 6, characterized in that, Ar1 and Ar2 may be the same as or different from each other, and each is independently selected from one of the following groups, whether substituted or unsubstituted: In any of the above groups, a carbon atom on any one and only one aromatic or heteroaromatic ring is a bonding site, and / or any hydrogen atom can be replaced by one of a deuterium or an alkyl group having 1 to 4 carbon atoms.

8. The triarylamine organic compound according to any one of claims 1 to 6, characterized in that, L0, L1, and L2 may be the same as or different from each other, and are each independently selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophene. The carbon atom on any two and only two of the aromatic or heteroaromatic rings in L0, L1, and L2 is a bonding site; the term "substitution" means that any hydrogen atom on the group can be replaced by one of deuterium, alkyl with 1 to 4 carbon atoms, deuterated alkyl with 1 to 4 carbon atoms, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl, methylphenyl, or tert-butylphenyl.

9. The triarylamine organic compound according to claims 1, 2, 3, 7, and 8, characterized in that, Triarylamine organic compounds are selected from any of the following chemical structures:

10. The triarylamine organic compound according to claims 1, 2, 5, 7, and 8, characterized in that, Triarylamine organic compounds are selected from any of the following chemical structures:

11. The triarylamine organic compound according to claims 1, 2, 6, 7, and 8, characterized in that, Triarylamine organic compounds are selected from any of the following chemical structures:

12. An organic electroluminescent material comprising a triarylamine organic compound according to any one of claims 1 to 11.

13. The triarylamine organic compound according to any one of claims 1 to 11, characterized in that, Its application is as a functional material in organic electronic devices, including organic electroluminescent devices, organic thin-film transistors, organic solar cells, organic-inorganic hybrid solar cells, optical sensors, radio frequency identification tags, or electronic paper.

14. An organic electroluminescent device, comprising a first electrode, a second electrode, and one or more functional layers located between the first electrode and the second electrode, wherein the functional layers contain a triarylamine organic compound as described in any one of claims 1-11.

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