Phosphonium salt derivatives and light emitting devices thereof

Abstract

The application belongs to the technical field of organic photoelectric materials, and particularly relates to a phosphonium salt derivative and a light-emitting device containing the same. The material takes a phosphonium positive ion as an electron acceptor unit, can be applied to the fields of photoluminescence and electroluminescence, and can emit ultraviolet light, visible light or infrared light. The application first constructs a TADF material by taking a phosphonium positive ion as an electron acceptor unit, and the obtained TADF material has excellent performance and is suitable for being used as an electroluminescent material to prepare a high-performance OLED device.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronic materials technology, specifically relating to a phosphine salt derivative and a light-emitting device containing it. Background Technology

[0002] Due to their characteristics such as flexibility, self-illumination, low driving voltage, fast response speed, wide viewing angle, and rich colors, organic light-emitting diodes (OLEDs) have attracted widespread attention from academia and industry over the past three decades, becoming a new generation of lighting and display technologies that are being developed internationally. Organic optoelectronic materials, especially luminescent materials, are the core components of organic light-emitting diodes. The research and development of efficient, stable, low-cost, and easily fabricated organic optoelectronic materials is important and urgent.

[0003] To improve the performance of organic light-emitting devices and advance their industrialization, various high-performance organic light-emitting material systems have been extensively developed, mainly including the following categories: fluorescent materials, noble metal phosphorescent materials, and thermally activated delayed fluorescence (TADF) materials. Among them, TADF materials possess a relatively small lowest singlet-triplet excited-state bandgap ΔE. ST Triplet excitons can transform into singlet excitons through antisystem crossing to emit light, achieving a quantum efficiency of up to 100% within the device. This makes it a low-cost, high-efficiency organic electroluminescent material. However, for commercial application, the stability of organic electroluminescent devices based on TADF materials needs further improvement, with the key lying in the development of novel high-performance TADF materials.

[0004] The fabrication processes for organic electroluminescent device panels mainly include thermal evaporation and wet processes (inkjet printing, screen printing, etc.). Compared with thermal evaporation, wet processes such as inkjet printing have advantages such as low energy consumption, short cycle time, convenient operation, high raw material utilization, and ease of achieving large-area roll-to-roll products. However, this process is not yet mature enough, especially since high-performance organic optoelectronic materials suitable for wet processes are relatively scarce and urgently need to be developed. Summary of the Invention

[0005] To solve the above-mentioned technical problems, the present invention provides a quaternary phosphine salt derivative having the structure shown in formula (I), formula (II), or formula (III):

[0006]

[0007]

[0008] in:

[0009] X1, X2, X3, and X4 may be the same or different, and are independently selected from unsubstituted or optionally substituted groups of one, two, or more Ra, including the following groups: C 1-20 Alkyl, C 3-20Cycloalkyl, 3-20 membered heterocyclic groups, C 6-40 Aryl, 5-40 heteroaryl;

[0010] n is an integer selected from 1 to 5;

[0011] Ra is selected from the following groups, either unsubstituted or optionally substituted by one, two or more Rs: C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 1-20 Alkoxy, 5-40 membered heteroaryl, C 6-40 Aryl, -N(5-40 heteroaryl)2, -N(C 6-40 Aryl)2;

[0012] Rs is selected from C 1-20 Alkyl, 5-40 membered heteroaryl, C 6-40 Aryl;

[0013] When Ra and Rs are the same or different, they are independently selected from 5-40 heteroaryl groups or C. 6-40 In the aryl form, Rs can be optionally connected to Ra to form a spiro ring;

[0014] The Rs is a 5-40 member heteroaryl group or C 6-40 When aryl, it can be further selectively subjected to C. 1-20 Alkyl substitution;

[0015] L is selected from the following groups that are unsubstituted or optionally substituted by one, two or more Rb groups: -C 6-40 Aryl-OC 6-40 Aryl-, 5-40 quinone heteroaryl, C 1-20 Alkylene, C 6-40 Alpha-aryl, -C 6-40 Aryl-C 6-40 aryl-, -5-40-aryl-5-40-aryl-;

[0016] Rb is selected from C 1-20 Alkyl or halogenated C 1-20 alkyl;

[0017] Y is selected from P, N, and C. 6-40 Aryl or 5-40 heteroaryl, wherein C 6-40 The aryl or 5-40 heteroaryl groups also contain 2, 3, 4 or 5 substitution sites that are independent of each other;

[0018] m is selected from integers from 1 to 5;

[0019] p is an integer selected from 3 to 6;

[0020] In equation (III), the number of anions is the product of m and p;

[0021] In the three general formulas, A - The anions, whether identical or different, are independently selected from monovalent anions, the total valence of which is such that the compound is electrically neutral.

[0022] According to an embodiment of the present invention, X1, X2, X3, and X4 may be the same or different, and are independently selected from C. 1-6 Alkyl, C 3-12 Cycloalkyl, 3-12 membered heterocyclic groups, unsubstituted or optionally substituted by one, two or more Ra groups, including the following groups: C 6-30 Aryl, 5-30 heteroaryl;

[0023] Ra is selected from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 1-6 Alkoxy groups, unsubstituted groups, or optionally substituted with one, two, or more Rs, including 5-30 membered heteroaryl groups, C 6-30 Aryl, -N(5-30 heteroaryl)2, -N(C 6-30 Aryl)2;

[0024] Rs is selected from C 1-6 Alkyl, 5-30 membered heteroaryl, C 6-30 Aryl;

[0025] When Ra and Rs are selected from 5-30 heteroaryl groups or C 6-30 In the aryl form, Rs can be optionally connected to Ra to form a spiro ring;

[0026] The Rs is a 5-30 member heteroaryl group or C 6-30 When aryl, it can be further selectively subjected to C. 1-6 Alkyl substitution;

[0027] n is 1, 2, 3 or 4;

[0028] L is selected from the following groups that are unsubstituted or optionally substituted by one, two or more Rb groups: -C 6-30 Aryl-OC 6-30 Aryl-, 5-30 quinone heteroaryl, C 1-6 Alkylene, C 6-30 Alpha-aryl, -C 6-30 Aryl-C 6-30 aryl-, -5-30-aryl-5-30-aryl-;

[0029] Rb is selected from C 1-6 Alkyl or halogenated C 1-6 alkyl;

[0030] Y is selected from P, N, and C. 6-30 Aryl or 5-30 heteroaryl, wherein C6-30 The aryl or 5-30 membered heteroaryl group also has 2, 3 or 4 substitution sites that are independent of each other;

[0031] m is 1 or 2; p is 1 or 2.

[0032] According to a preferred embodiment of the present invention, X1, X2, and X3 may be the same or different, and are independently selected from unsubstituted or optionally substituted by one, two or more Ra groups, namely: phenyl, naphthyl, cyclohexyl, n-butyl;

[0033] X4 and Ra may be the same or different, and are independently selected from methyl, methoxy, trifluoromethyl, acridine, dimethylacridyl, tert-butyl-substituted acridine, phenyl-substituted acridine, carbazolyl, dimethylcarbazolyl, tert-butyl-substituted carbazolyl, phenyl-substituted carbazolyl, N-phenyl-substituted carbazolyl, dibenzothiophene, dibenzofuran, phenthiazinyl, phenoxazinyl, phenazinyl, -N(tert-butyl-substituted phenyl)2 or the following groups:

[0034]

[0035] The asterisk (*) indicates a connection point.

[0036] n is 1, 2, or 3;

[0037] L is selected from -phenyl-O-phenyl-, dimethyloxanthyl, methylene, di-trifluoromethyl substituted methylene, ethylene, propylene, butylene, phenylene, biphenylene, or naphthylene.

[0038] m is 1 or 2;

[0039] p is 3;

[0040] Y is selected from P, N,

[0041] A - The anion corresponding to the phosphonium cation in a quaternary phosphonium salt is selected from at least one of the following structures: PF6 - BF4 - ,

[0042]

[0043] As an example, the positive ion moiety in the quaternary phosphine salt derivative of formula (I) is selected from one of the following structures:

[0044]

[0045]

[0046]

[0047]

[0048] As an example, the positive ion moiety in the quaternary phosphine salt derivative of formula (II) is selected from one of the following structures:

[0049]

[0050]

[0051] As an example, the positive ion moiety in the quaternary phosphine salt derivative of formula (III) is selected from one of the following structures:

[0052]

[0053]

[0054] The present invention also provides the use of one, two or three of the quaternary phosphine salt derivatives of formula (I), or formula (II), or formula (III) as described above in the preparation of light-emitting devices.

[0055] According to embodiments of the present invention, the quaternary phosphine salt derivative has photoluminescent or electroluminescent properties and can emit ultraviolet, visible, or infrared light. Preferably, the quaternary phosphine salt compound is a thermally activated delayed fluorescence material.

[0056] According to an embodiment of the present invention, the light-emitting device is an organic light-emitting diode or a luminescent electrochemical cell.

[0057] The present invention also provides a light-emitting device comprising two electrodes and a functional layer located between the electrodes, wherein the functional layer comprises one, two or more of the quaternary phosphine salt derivatives shown in formula (I), formula (II), or formula (III) above.

[0058] Preferably, the functional layer is one, two or more of the following: an injection layer, a transport layer, a light-emitting layer, and a blocking layer.

[0059] Preferably, the quaternary phosphine salt derivative represented by formula (I), formula (II), or formula (III) is located in the luminescent layer.

[0060] Preferably, the light-emitting device includes a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode.

[0061] The present invention also provides a method for fabricating the light-emitting device as described above, comprising the following steps: sequentially disposing of an anode, a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode on a substrate.

[0062] Preferably, the anode, hole injection layer, hole transport layer, light-emitting layer, hole blocking layer, electron transport layer, electron injection layer and cathode are configured by spin coating, inkjet printing or vapor deposition, for example by inkjet printing.

[0063] Beneficial effects:

[0064] 1. This invention provides a class of quaternary phosphine salt derivatives, which use phosphine cations as electron acceptor units and can be applied in the fields of photoluminescence and electroluminescence, emitting ultraviolet light, visible light or infrared light.

[0065] 2. Using the compound provided by this invention as the light-emitting layer in an electroluminescent device, the resulting electroluminescent device exhibits excellent device performance, with the following specific advantages:

[0066] (1) This invention is the first to construct TADF material using phosphine ions as electron acceptor units. The resulting TADF material has excellent performance (excellent luminescence performance, film formation and thermal stability) and is suitable as an electroluminescent material to prepare high-performance OLED devices.

[0067] (2) Compared with commercial iridium complexes, the preparation process of the quaternary phosphine salt compound described in this invention is simple, the raw materials used for synthesis are readily available and inexpensive, and the electroluminescent devices prepared have excellent performance (stable luminous color, high luminous efficiency and small device efficiency roll-off).

[0068] (3) The quaternary phosphine salt derivatives described in this invention are readily soluble in various solvents and are very suitable for preparing high-performance light-emitting devices using wet processes, and have industrialization prospects.

[0069] Terminology Definitions and Explanations

[0070] Unless otherwise stated, the definitions of groups and terms recorded in this application specification and claims, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, and definitions of specific compounds in the examples, can be arbitrarily combined and combined with each other. Such combinations and combinations of group definitions and compound structures shall fall within the scope of protection of this application.

[0071] The numerical ranges described in this application specification and claims, when the range can only be "integers", should be understood to include the two endpoints of the range and every integer within the range. For example, the number of carbon atoms "1 to 5" should be understood to include every integer of 1, 2, 3, 4, and 5.

[0072] "More than three" means three or more types.

[0073] The term "halogen" as used in this invention refers to fluorine, chlorine, bromine, and iodine.

[0074] Term "C"1-20 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably C. 1-10 Alkyl group. "C" 1-10 "Alkyl" should be understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc., or isomers thereof. In particular, the group has 1, 2, 3, 4, 5, or 6 carbon atoms ("C"). 1-6 Alkyl groups, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and more particularly, the groups having 1, 2, or 3 carbon atoms (“C”). 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.

[0075] Term "C" 3-20 "Cycloalkyl" should be understood to refer to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C". 3-10 cycloalkyl. The term "C" 3-10 "Cycloalkyl" should be understood to refer to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The C... 3-10 Cycloalkyl groups can be monocyclic hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or bicyclic hydrocarbon groups such as decahydronaphthalene ring.

[0076] The term "3-20 membered heterocyclic group" refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O, and S, preferably a "3-10 membered heterocyclic group". The term "3-10 membered heterocyclic group" refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3, heteroatoms selected from N, O, and S. The heterocyclic group can be connected to the rest of the molecule via any one of the carbon atoms or a nitrogen atom (if present). Specifically, the heterocyclic group can include, but is not limited to: 4-membered rings, such as azirrobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoalkyl, pyrazolyl, or pyrrololinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl, or trithiaalkyl; or 7-membered rings, such as diazacycloheptyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopentano[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The nitrogen-containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, for example, but not limited to, 2,5-dihydro-1H-pyrrole, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic group is non-aromatic. The term "C" is used to describe the non-aromatic nature of the heterocyclic group. 6-40 "Aryl" should be understood to refer to a monocyclic, bicyclic, tricyclic, or more cyclic hydrocarbon ring having 6 to 40 carbon atoms and exhibiting monovalent aromaticity or partial aromaticity. Preferably, "C" is used. 6-14 "Aromatic", the term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. The "more cyclic hydrocarbon rings" are, for example, C10. 15～30 Cyclic hydrocarbon ring.

[0077] The term "5-40-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, tricyclic aromatic ring systems or more aromatic ring systems having 5 to 40 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, for example, "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O, and S, and in each case, may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc. The "more aromatic ring system" is, for example, a 15-30 membered cyclic aromatic ring system containing 1-5 heteroatoms independently selected from N, O and S.

[0078] Unless otherwise stated, heterocyclic, heteroaryl, or heteroaryl groups include all their possible isomers, such as their positional isomers. Thus, for some illustrative, non-limiting examples, pyridyl or pyridylene includes pyridin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thiophenyl or thiophene includes thiophene-2-yl, thiophene-2-yl, thiophene-3-yl, and thiophene-3-yl.

[0079] The above refers to the term "C" 1-20 The definition of "alkyl" also applies to compounds containing "C". 1-20 Other terms for "alkyl", such as the term "C 1-20 Alkoxy, halogenated C 1-20 Alkyl groups, etc. Attached Figure Description

[0080] Figure 1 The steady-state photoluminescence spectra of compounds (compound 1 [PF6] and compound 68 [PF6]) of Examples 1 and 5 of the present invention, doped at a concentration of 30 wt% in the host material 2,6-dicarbazole-1,5-pyridine (PYD2) thin film.

[0081] Figure 2 The steady-state photoluminescence spectra of compounds (compound 83 [BF4] and compound 84 [BF4]) of Examples 6 and 7 of the present invention, doped at a concentration of 30 wt% in the host material PYD2 thin film.

[0082] Figure 3 The transient spectra of compounds (compound 1 [PF6], 68 [PF6], 83 [BF4] and 84 [BF4]) of Examples 1 and 5-7 of the present invention, doped at a concentration of 30 wt% in the host material PYD2 thin film.

[0083] Figure 4 The image shows the atomic force microscopy results of the thin films of the host material PYD2 doped with compounds (compound 1 [PF6] and compound 68 [PF6]) of Examples 1 and 5 of the present invention at a concentration of 30 wt%.

[0084] Figure 5 Thermogravimetric analysis (TGA) curves of compounds (compound 1 [PF6] and compound 68 [PF6]) in Examples 1 and 5 of this invention.

[0085] Figure 6 Thermogravimetric analysis (TGA) curves of compounds (compound 83 [BF4] and compound 84 [BF4]) in Examples 6 and 7 of this invention.

[0086] Figure 7 The electroluminescence spectra of the organic electroluminescent devices (OLED-1 and OLED-5) of Embodiments 12 and 16 of the present invention at different driving voltages are shown.

[0087] Figure 8 The efficiency-brightness curves of the organic electroluminescent devices (OLED-1 and OLED-5) of Examples 12 and 16 of the present invention are shown.

[0088] Figure 9 The efficiency-brightness curves of the organic electroluminescent devices (OLED-6 and OLED-7) of Examples 17 and 18 of the present invention are shown. Detailed Implementation

[0089] The following detailed description, in conjunction with specific embodiments, illustrates the general formula compounds of the present invention, their preparation methods, and applications in further detail. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0090] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0091] The synthetic routes of compounds 1[Br] and 1[PF6] in Example 1 are shown below:

[0092]

[0093] [Synthesis of intermediate compound DMAC-PhBr]

[0094] In a dry Schlenk flask, 1-bromo-4-iodobenzene (6.22 g, 22 mmol), 9,9-dimethyl-acridine (4.19 g, 20 mmol), cuprous iodide (0.76 g, 4 mmol), sodium tert-butoxide (3.84 g, 40 mmol), (1S,2S)-(+)-1,2-cyclohexanediamine (0.23 g, 2 mmol), and dried 1,4-dioxane (30 mL) were added. The reaction mixture was stirred and refluxed under argon protection for 12 hours, then cooled to room temperature and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a white solid (5.46 g, 75% yield). MS: m / z 363.0623 [M] + ]; Elemental analysis: C 21 H 18 BrN, calculated values ​​(%): C, 69.24; H, 4.98; N, 3.85; measured values: C 69.26; H 4.97; N, 3.85.

[0095] [Synthesis of Compound 1 [Br]]

[0096] In a high-pressure reaction tube, intermediate compound DMAC-PhBr (3 mmol, 1.09 g), triphenylphosphine (3.15 mmol, 0.83 g), nickel bromide (0.6 mmol, 0.131 g), and ethylene glycol (6 mL) were added. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The purified solid was obtained by column chromatography (1.65 g, 88% yield). MS (m / z, cationic fraction): 546.2346 [M] + Elemental analysis: C 39 H 33 BrNP, calculated values ​​(%): C, 74.76; H, 5.31; N, 2.24; measured values: C 74.79; H 5.43; N, 2.15.

[0097] [Synthesis of Compound 1 [PF6]]

[0098] A solution (5 mL) of Ag[PF6] (1 mmol, 0.253 g) in acetone was added to a solution (10 mL) of compound 1 [Br] (1 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a pale yellow solid (0.622 g, 90% yield). MS (m / z, cationic fraction): 546.2346 [M] + Elemental analysis: C 39 H 33 F6NP2, calculated (%): C, 67.73; H, 4.81; N, 2.03; measured: C 67.76; H 4.93; N, 2.00. Compound 1 [PF6], doped at a mass concentration of 30 wt% in a polymeric polymethyl methacrylate film, exhibits a photoluminescence efficiency of up to 75%.

[0099] The synthetic routes of compounds 21[Br] and 21[PF6] in Example 2 are shown below:

[0100]

[0101] [Synthesis of intermediate compound 2Cz-PhBr]

[0102] Under a nitrogen atmosphere, 2,5-difluorobromobenzene (1.93 g, 10 mmol), carbazole (3.34 g, 20 mmol), and cesium carbonate (13 g, 8 mmol) were added to 30 mL of N,N-dimethylformamide (DMF). The mixture was stirred at 150 °C for 12 hours, then poured into 400 mL of water. The precipitate was collected by filtration. Column purification yielded a white solid (3.90 g, yield: 80%). MS: m / z 486.0732 [M] + ]; Elemental analysis: C 30 H 19 BrN2, calculated values ​​(%): C, 73.93; H, 3.93; N, 5.75; measured values: C 73.94; H 3.97; N, 5.75.

[0103] [Synthesis of compound 21 [Br]]

[0104] Intermediate compound 2Cz-PhBr (3 mmol, 1.46 g), triphenylphosphine (3.15 mmol, 0.83 g), nickel bromide (0.6 mmol, 0.131 g), and ethylene glycol (6 mL) were added to a high-pressure reaction tube. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a pale yellow solid (1.91 g, 85% yield). MS (m / z, cationic fraction): 669.2455 [M] + Elemental analysis: C 48 H 34 BrN2P, calculated values ​​(%): C, 76.90; H, 4.57; N, 3.74; measured values: C 76.92; H 4.66; N, 3.72.

[0105] [Synthesis of Compound 21 [PF6]]

[0106] A solution (5 mL) of Ag[PF6] (1 mmol, 0.253 g) in acetone was added to a solution (10 mL) of compound 21[Br] (1 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a pale yellow solid (0.75 g, yield 92%). MS (m / z, cationic fraction): 669.2455 [M] + Elemental analysis: C 48 H 34 F6N2P2, calculated values ​​(%): C, 70.76; H, 4.21; N, 3.44; measured values: C 70.78; H 4.27; N, 3.44.

[0107] Example 3

[0108] The synthetic routes for compounds 29[Br] and 29[B(Ph(CF3)2)4] are shown below:

[0109]

[0110] [Synthesis of Compound 29 [Br]]

[0111] The intermediate compound DMAC-PhBr (3 mmol, 1.09 g), tricyclohexylphosphine (3.15 mmol, 0.88 g), nickel bromide (0.6 mmol, 0.131 g), and ethylene glycol (6 mL) prepared in Example 1 were added to a high-pressure reaction tube. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a white solid (1.60 g, 83% yield). MS (m / z, cationic fraction): 564.3754 [M] + Elemental analysis: C 39 H 33 BrNP, calculated values ​​(%): C, 72.66; H, 7.97; N, 2.17; measured values: C 72.68; H 8.02; N, 2.16.

[0112] [Synthesis of compound 29 [B(Ph(CF3)2)4]]

[0113] A solution (5 mL) of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (1 mmol, 0.886 g) in acetone was added to a solution (10 mL) of compound 29[Br] (1 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a pale yellow solid (1.13 g, yield 79%). MS (m / z, cationic fraction): 564.3754 [M] + Elemental analysis: C 71 H 63 BF 24 NP, calculated values ​​(%): C, 59.72; H, 4.45; N, 0.98; measured values: C 59.76; H 4.49; N, 0.95.

[0114] Example 4

[0115] The synthetic routes for compounds 54[Br] and 54[PF6] are shown below:

[0116]

[0117] [Synthesis of intermediate compound 3Cz-PhBr]

[0118] The intermediate compound 3Cz-PhBr was synthesized according to the method disclosed in the literature [Journal of Materials Chemistry C, 2017, 5, 9753-9760].

[0119] [Synthesis of Compound 54 [Br]]

[0120] In a high-pressure reaction tube, intermediate compound 3Cz-PhBr (1 mmol, 0.877 g), tri-n-butylphosphine (1.05 mmol, 0.28 g), nickel bromide (0.2 mmol, 43.7 mg), and ethylene glycol (3 mL) were added. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The purified solid was obtained by column chromatography (0.863 g, 78% yield). MS (m / z, cationic fraction): 998.6476 [M] + Elemental analysis: C 70 H 85 BrN3P, calculated values ​​(%): C, 77.90; H, 7.94; N, 3.89; measured values: C 78.15; H 8.25; N, 3.70.

[0121] Synthesis of Compound 54 [PF6]

[0122] A solution (3 mL) of Ag[PF6] (0.5 mmol, 0.127 g) in acetone was added to a solution (6 mL) of compound 54[Br] (0.5 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a white solid (0.52 g, yield 89%). MS (m / z, cationic fraction): 998.6476 [M] + Elemental analysis: C 70 H 85 F6N3P2, calculated values ​​(%): C, 73.47; H, 7.49; N, 3.67; measured values: C 73.79; H 7.76; N, 3.49.

[0123] The synthetic routes for compounds 68[Br] and 68[PF6] in Example 5 are shown below:

[0124]

[0125] [Synthesis of intermediate compound DMAC-PPh3]

[0126] Under argon protection, an anhydrous tetrahydrofuran solution of the intermediate compound DMAC-PhBr (1.82 g, 5 mmol) was cooled to -78 °C, and n-butyllithium (2.5 M, 5.5 mmol, 2.2 mL) was slowly added dropwise. The mixture was stirred at -78 °C for 2 hours, and then diphenylphosphine chloride (1.10 g, 5 mmol) was added dropwise. The mixture was slowly heated to room temperature and stirred for 12 hours at room temperature. The mixture was then quenched with methanol, the solvent was evaporated, and the solution was purified by column chromatography to give a white solid (1.93 g, 82% yield). MS (m / z): 469.1959 [M] + Elemental analysis: C 33 H 28 NP, calculated values ​​(%): C, 84.41; H, 6.01; N, 2.98; measured values: C 84.41; H 6.03; N, 2.97.

[0127] [Synthesis of Compound 68 [Br]]

[0128] Intermediate compounds DMAC-PhBr (3 mmol, 1.09 g), DMAC-PPh3 (3.15 mmol, 1.48 g), nickel bromide (0.6 mmol, 0.131 g), and ethylene glycol (6 mL) were added to a high-pressure reaction tube. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and purified by column chromatography after solvent removal to give a pale yellow solid (1.9 g, 76% yield). MS (m / z, cationic fraction): 753.3393 [M] + Elemental analysis: C 54 H 46 BrN2P, calculated values ​​(%): C, 77.78; H, 5.56; N, 3.36; measured values: C 77.82; H 5.63; N, 3.31.

[0129] Synthesis of Compound 68 [PF6]

[0130] A solution (5 mL) of Ag[PF6] (1 mmol, 0.253 g) in acetone was added to a solution (10 mL) of compound 68[Br] (1 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a pale yellow solid (0.773 g, yield 86%). MS (m / z, cationic fraction): 753.3393 [M] + Elemental analysis: C 54 H 46F6N2P2, calculated values ​​(%): C, 72.15; H, 5.16; N, 3.12; measured values: C 72.18; H 5.26; N, 3.15. Compound 68 [PF6], doped at a mass concentration of 30 wt% in a polymeric polymethyl methacrylate film, exhibits a photoluminescence efficiency of up to 91%.

[0131] Example 6 Synthesis of compound 83 [Br] and compound 83 [BF4]

[0132]

[0133] [Synthesis of intermediate compound DBF-PPh2]

[0134] Under argon protection, an anhydrous tetrahydrofuran solution of 2-bromodibenzofuran (1.23 g, 5 mmol) was cooled to -78 °C, and n-butyllithium (2.5 M, 5.5 mmol, 2.2 mL) was slowly added dropwise. The mixture was stirred at -78 °C for 2 hours, and then diphenylphosphine chloride (1.10 g, 5 mmol) was added dropwise. The mixture was slowly heated to room temperature and stirred for 12 hours at room temperature. The mixture was then quenched with methanol, the solvent was evaporated, and the solution was purified by column chromatography to give a white solid (1.65 g, 94% yield). MS (m / z): 352.3728 [M] + Elemental analysis: C 24 H 17 OP, calculated values ​​(%): C, 81.81; H, 4.86; O, 4.54; measured values: C, 81.50; H, 4.92; O, 4.63.

[0135] [Synthesis of Compound 83[Br]]

[0136] Intermediate compounds DMAC-PhBr (3 mmol, 1.09 g), DBF-PPh2 (3.15 mmol, 1.11 g), nickel bromide (0.6 mmol, 0.131 g), and ethylene glycol (6 mL) were added to a high-pressure reaction tube. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The purified solid was obtained by column chromatography (1.8 g, 85% yield). MS (m / z, cationic fraction): 636.2451 [M] + Combustion-based elemental analysis: C 45 H 35 BrNPO, calculated values ​​(%): C, 75.42; H, 4.92; N, 1.95; measured values: C, 75.51; H, 4.98; N, 1.97.

[0137] [Synthesis of Compound 83 [BF4]]

[0138] A solution (5 mL) of Ag[BF4] (1 mmol, 0.195 g) in acetone was added to a solution (10 mL) of compound 83[Br] (1 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a pale yellow solid (0.59 g, yield 81%). MS (m / z, cationic fraction): 636.2451 [M] + Combustion-based elemental analysis: C 45 H 35 BF4NPO, calculated values ​​(%): C, 74.70; H, 4.88; N, 1.94; measured values: C, 74.19; H, 5.08; N, 1.86.

[0139] Example 7

[0140] Synthesis of Compound 84[Br] and Compound 84[BF4]

[0141]

[0142] [Synthesis of intermediate compound DBT-PPh2]

[0143] Under argon protection, an anhydrous tetrahydrofuran solution of 2-bromodibenzothiophene (1.31 g, 5 mmol) was cooled to -78 °C, and n-butyllithium (2.5 M, 5.5 mmol, 2.2 mL) was slowly added dropwise. The mixture was stirred at 78 °C for 2 hours, and then diphenylphosphine chloride (1.10 g, 5 mmol) was added dropwise. The mixture was slowly heated to room temperature and stirred for 12 hours at room temperature. The mixture was then quenched with methanol, the solvent was evaporated, and the solution was purified by column chromatography to give a white solid (1.65 g, 93% yield). MS (m / z): 368.0789 [M] + Elemental analysis: C 24 H 17 PS, Calculated values ​​(%): C, 78.24; H, 4.65; S, 8.70; Measured values: C, 78.45; H, 4.82; S, 8.46.

[0144] [Synthesis of Compound 84[Br]]

[0145] Intermediate compounds DMAC-PhBr (3 mmol, 1.09 g), DBT-PPh2 (3.15 mmol, 1.16 g), nickel bromide (0.6 mmol, 0.131 g), and ethylene glycol (6 mL) were added to a high-pressure reaction tube. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The purified solid was obtained by column chromatography (1.8 g, 85% yield). MS (m / z, cationic fraction): 652.2223 [M] + Combustion-based elemental analysis: C 45 H 35 BrNPS, calculated values ​​(%): C, 73.77; H, 4.81; N, 1.91; measured values: C, 73.55; H, 4.82; N, 1.88.

[0146] [Synthesis of Compound 84 [BF4]]

[0147] A solution (5 mL) of Ag[BF4] (1 mmol, 0.195 g) in acetone was added to a solution (10 mL) of compound 84[Br] (1 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a pale yellow solid (0.63 g, yield 85%). MS (m / z, cationic fraction): 652.2223 [M] + Combustion-based elemental analysis: C 45 H 35 BF4NPS, calculated values ​​(%): C, 73.08; H, 4.77; N, 1.89; measured values: C, 72.42; H, 5.26; N, 1.97.

[0148] The synthetic routes of compounds 101[Br] and 101[PF6] in Example 8 are shown below:

[0149]

[0150] [Synthesis of the intermediate compound SFAC-PhBr]

[0151] In a dry Schlenk flask, 1-bromo-4-iodobenzene (6.22 g, 22 mmol), 10H-spiro[acridin-9,9'-fluorene] (6.62 g, 20 mmol), cuprous iodide (0.76 g, 4 mmol), sodium tert-butoxide (3.84 g, 40 mmol), (1S,2S)-(+)-1,2-cyclohexanediamine (0.23 g, 2 mmol), and dried 1,4-dioxane (30 mL) were added. The reaction mixture was stirred and refluxed under argon protection for 12 hours, then cooled to room temperature and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a white solid (6.61 g, 68% yield). MS: m / z 485.0779 [M] + ]; Elemental analysis: C 31 H 20 BrN, calculated values ​​(%): C, 76.55; H, 4.14; N, 2.88; measured values: C 76.55; H 4.15; N, 2.85.

[0152] [Synthesis of intermediate compound 2SFAC-PPh3]

[0153] Under argon protection, an anhydrous tetrahydrofuran solution of the intermediate compound SFAC-PhBr (2.43 g, 5 mmol) was cooled to -78 °C, and n-butyllithium (2.5 M, 5.5 mmol, 2.2 mL) was slowly added dropwise. The mixture was stirred at -78 °C for 2 hours, and then phenylphosphine dichloride (0.448 g, 2.5 mmol) was added dropwise. The mixture was slowly heated to room temperature and stirred for 12 hours at room temperature. The mixture was quenched with methanol, the solvent was evaporated, and the solution was purified by column chromatography to give a white solid (1.77 g, 77% yield). MS (m / z): 920.3320 [M] + Elemental analysis: C 68 H 45 N2P, calculated values ​​(%): C, 88.67; H, 4.92; N, 3.04; measured values: C 88.71; H 5.00; N, 3.02.

[0154] [Synthesis of Compound 101 [Br]]

[0155] In a high-pressure reaction tube, intermediate compounds SFAC-PhBr (1 mmol, 0.486 g), 2SFAC-PPh3 (1.05 mmol, 0.967 g), nickel bromide (0.2 mmol, 43.7 mg), and ethylene glycol (3 mL) were added. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a yellow solid (0.94 g, 67% yield). MS (m / z, cationic fraction): 1327.4945 [M] + Elemental analysis: C 99 H 65 BrN3P, calculated values ​​(%): C, 84.48; H, 4.66; N, 2.99; measured values: C 84.61; H 4.73; N, 3.03.

[0156] [Synthesis of Compound 101 [PF6]]

[0157] A solution (3 mL) of Ag[PF6] (0.5 mmol, 0.127 g) in acetone was added to a solution (6 mL) of compound 101[Br] (0.5 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a yellow solid (0.648 g, 88% yield). MS (m / z, cationic fraction): 1327.4945 [M] + Elemental analysis: C 99 H 65 F6N3P2, Calculated values ​​(%): C, 80.75; H, 4.45; N, 2.85; Measured values: C 80.82; H 4.63; N, 2.75.

[0158] The synthetic routes for compounds 103[Br] and 103[PF6] in Example 9 are shown below:

[0159]

[0160] [Synthesis of intermediate compound 3DMAC-PPh3]

[0161] Under argon protection, an anhydrous tetrahydrofuran solution of the intermediate compound DMAC-PhBr (2.73 g, 7.5 mmol) was cooled to -78 °C, and then n-butyllithium (2.5 M, 8.25 mmol, 3.3 mL) was slowly added dropwise. The mixture was stirred at -78 °C for 2 hours, and then phosphorus trichloride (0.343 g, 2.5 mmol) was added dropwise. The mixture was slowly heated to room temperature and stirred for 12 hours at room temperature. The mixture was then quenched with methanol, the solvent was evaporated, and the solution was purified by column chromatography to give a white solid (1.48 g, 67% yield). MS (m / z): 883.4055 [M] + Elemental analysis: C 63 H 54 N3P, calculated values ​​(%): C, 85.59; H, 6.16; N, 4.75; measured values: C, 85.57; H, 6.14; N, 4.76.

[0162] [Synthesis of Compound 103[Br]]

[0163] In a high-pressure reaction tube, intermediate compounds DMAC-PhBr (1 mmol, 0.363 g), 3DMAC-PPh3 (1.05 mmol, 0.928 g), nickel bromide (0.2 mmol, 43.7 mg), and ethylene glycol (3 mL) were added. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a yellow solid (0.84 g, 67% yield). MS (m / z, cationic fraction): 1167.5490 [M] + Elemental analysis: C 84 H 72 BrN4P, calculated values ​​(%): C, 80.82; H, 5.81; N, 4.49; measured values: C, 80.89; H, 5.90; N, 4.52.

[0164] [Synthesis of Compound 103 [PF6]]

[0165] A solution (3 mL) of Ag[PF6] (0.5 mmol, 0.127 g) in acetone was added to a solution (6 mL) of compound 103[Br] (0.5 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a yellow solid (0.558 g, yield 85%). MS (m / z, cationic fraction): 1167.5490 [M] + Elemental analysis: C 84 H 72F6N4P2, calculated values ​​(%): C, 76.81; H, 5.53; N, 4.27; measured values: 76.89; H, 5.64; N, 4.21.

[0166] The synthetic routes of compounds 114[2Br] and 114[2PF6] in Example 10 are shown below:

[0167]

[0168] Synthesis of intermediate compound DMAC-POP[Br]

[0169] In a high-pressure reaction tube, intermediate compound DMAC-PhBr (3 mmol, 1.09 g), bis(2-diphenylphosphine) ether (3.15 mmol, 1.70 g), nickel bromide (0.6 mmol, 0.131 g), and ethylene glycol (6 mL) were added. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The purified solid was obtained by column chromatography (2.19 g, 81% yield). MS (m / z, cationic fraction): 822.3050 [M] + Elemental analysis: C 57 H 46 BrNP2O, calculated values ​​(%): C, 75.83; H, 5.14; N, 1.55; measured values: C, 75.81; H, 5.13; N, 1.57.

[0170] [Synthesis of compound 114[2Br]]

[0171] p-Bromobenzazole (1 mmol, 0.322 g), DMAC-POP[Br] (1.05 mmol, 0.947 g), nickel bromide (0.2 mmol, 43.7 mg), and ethylene glycol (3 mL) were added to a high-pressure reaction tube. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a pale yellow solid (1.04 g, 85% yield). MS (m / z, cationic fraction): 1064.4013 [M] + Elemental analysis: C 75 H 58 Br2N2OP2, calculated values ​​(%): C, 73.53; H, 4.77; N, 2.29; measured values: C, 73.57; H, 4.84; N, 2.25.

[0172] [Synthesis of Compound 114[2PF6]]

[0173] A solution (3 mL) of Ag[PF6] (1 mmol, 0.253 g) in acetone was added to a solution (6 mL) of compound 114[2Br] (0.5 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a pale yellow solid (0.549 g, yield 81%). MS (m / z, cationic fraction): 1064.4013 [M] + Elemental analysis: C 75 H 58 F 12 N2OP4, calculated values ​​(%): C, 66.47; H, 4.31; N, 2.07; measured values: C, 66.49; H, 4.38; N, 2.06.

[0174] The synthetic routes of compounds 134[3Br] and 134[3PF6] in Example 11 are shown below:

[0175]

[0176] [Synthesis of intermediate compound TRZ-TPP]

[0177] Tribromophenyl-1,3,5-triazine (5.46 g, 10 mmol), sodium acetate (2.7 g, 33 mmol), palladium acetate (67 mg, 0.3 mmol), diphenylphosphine (6 mL, 33 mmol), and N,N-dimethylformamide (DMF) (5 mL) were added to a reaction flask. Under argon protection, the reaction system was stirred at 130 °C for 24 hours and then cooled to room temperature. After multiple extractions with dichloromethane, the combined organic phases were washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The solution was purified by column chromatography to give a white solid (4.48 g, yield 52%). MS (m / z): 861.2592 [M] + Elemental analysis: C 57 H 42 N3P3, calculated values ​​(%): C, 79.43; H, 4.91; N, 4.88; measured values: C, 79.49; H, 5.03; N, 4.77.

[0178] [Synthesis of compound 134[3Br]]

[0179] Intermediate compounds DMAC-PhBr (3 mmol, 1.09 g), TRZ-TPP (1 mmol, 0.862 g), nickel bromide (0.6 mmol, 131 mg), and ethylene glycol (6 mL) were added to a high-pressure reaction tube. After several evacuations, the reaction system was heated to 180 °C and stirred for 12 hours under argon protection. The reaction mixture was then cooled to room temperature and extracted with dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous Na₂SO₄, and the solvent was evaporated. The purified solid was obtained by column chromatography (0.92 g, 47% yield). MS (m / z, cationic fraction): 1713.6893 [M] + Elemental analysis: C 120 H 96 Br3N6P3, calculated values ​​(%): C, 73.73; H, 4.95; N, 4.30; measured values: C, 73.77; H, 5.05; N, 4.24.

[0180] [Synthesis of Compound 134 [3PF6]]

[0181] A solution (3 mL) of Ag[PF6] (1 mmol, 0.253 g) in acetone was added to a solution (6 mL) of compound 134[3Br] (0.33 mmol) in dichloromethane, and the mixture was stirred at room temperature for 1.5 hours. The filtrate after filtration of the reaction mixture was evaporated to dryness and purified by column chromatography to give a yellow solid (0.546 g, 77% yield). MS (m / z, cationic fraction): 1713.6893 [M] + Elemental analysis: C 120 H 96 F 18 N6P6, calculated values ​​(%): C, 67.04; H, 4.50; N, 3.91; measured values: C, 67.08; H, 4.60; N, 3.90.

[0182] Example 12

[0183] Fabrication of organic electroluminescent device 1 (OLED-1) (in which compound 1 [PF6] accounts for 30% of its own mass and the total mass of commercially available host material PYD2).

[0184] In this embodiment, compound 1 [PF6] prepared in Example 1 is used as the luminescent material, commercially available host material PYD2 is used as the host material, indium tin oxide (ITO) is used as the anode, PEDOT:PSS is used as the hole injection material, TFB is used as the hole transport material, m4PO is used as the hole blocking material, TPBi is used as the electron transport material, LiF is used as the electron injection material, and aluminum (Al) is used as the cathode material to construct an electroluminescent device with the device structure of ITO / PEDOT:PSS / TFB / PYD2:compound 1 [PF6] (30wt%) / m4PO / TPBi / LiF / Al.

[0185] The fabrication process of the aforementioned electroluminescent device is as follows: A glass substrate with an ITO (100nm) transparent conductive layer is cleaned with alkaline solution and rinsed with deionized water. It is then ultrasonically treated in deionized water, acetone, and isopropanol for ten minutes sequentially. After baking in a clean environment until no solvent residue remains, it is treated with ultraviolet ozone for 15 minutes. A PEDOT:PSS solution is filtered and spin-coated onto the treated substrate to form a 30nm layer, and annealed at 150°C for 20 minutes as a hole injection layer (HIL). A TFB solution is spin-coated onto the PEDOT:PSS layer to form a 10nm layer, and annealed at 200°C for 20 minutes as a hole transport layer (HTL). A solution of the host material PYD2 and compound 1 [PF6] as the dopant luminescent material is spin-coated onto the TFB layer, with a doping mass ratio of 30wt%, and annealed at 60°C for 15 minutes to form a 40nm thick luminescent layer. The annealed substrate is placed in a vacuum chamber and evacuated to a vacuum level below 2×10⁻⁶. -5 Pa. On the light-emitting layer, m₄PO is deposited at a deposition rate of 0.2 nm / s to form a layer with a thickness of 8 nm, serving as a hole blocking layer (HBL). On the hole blocking layer, TPBi is deposited at a deposition rate of 0.2 nm / s to form a layer with a thickness of 45 nm, serving as an electron transport layer (ETL). On the electron transport layer, LiF is deposited at a deposition rate of 0.02 nm / s to form a layer with a thickness of 1 nm, serving as an electron injection layer (EIL). Finally, Al is deposited on the electron injection layer at a deposition rate of 0.5 nm / s to form a cathode with a thickness of 100 nm.

[0186] Examples 13-22

[0187] Fabrication of Organic Electroluminescent Devices 2-11 (OLED-2-11)

[0188] Except that compounds 21[PF6], 29[B(Ph(CF3)2)4], 54[PF6], 68[PF6], 83[BF4], 84[BF4], 101[PF6], 103[PF6], 114[2PF6] and 134[3PF6] described in Examples 2 to 11 were used as doped luminescent materials instead of compound 1[PF6] in Example 12, OLED-2 to 11 were prepared under the same production conditions as OLED-1.

[0189] Comparative Example I and Comparative Example II: Comparison of OLED-I and OLED-II fabrication:

[0190] Comparative OLED-I and Comparative OLED-II were prepared under the same production conditions as OLED-1, except that the commercially available iridium complex Flrpic or the known compound BP-DMAC were used as doped luminescent materials instead of compound 1 [PF6] in Example 12.

[0191] The method for forming each structural layer in the organic electroluminescent device of the present invention is not limited, and may include, but is not limited to, existing vacuum evaporation method, spin coating method and inkjet printing method.

[0192] The structures of the compounds involved in Examples 12-22 and Comparative Examples I-II are as follows:

[0193]

[0194] The current-voltage characteristics and luminescence characteristics of the organic light-emitting diodes in Examples 12-22 and Comparative Examples I-II were tested using characterization equipment, and important parameters such as external quantum efficiency and lifetime were recorded (test results are shown in Table 1).

[0195] As shown in Table 1, compared with the light-emitting devices of Comparative Example I and Comparative Example II that used the commercial iridium complex Flrpic and the known compound BP-DMAC as doped light-emitting materials, the light-emitting devices of Examples 12-22 that used compounds 1[PF6], 21[PF6], 29[B(Ph(CF3)2)4], 54[PF6], 68[PF6], 83[BF4], 84[BF4], 101[PF6], 103[PF6], 114[2PF6], and 134[3PF6] as doped light-emitting materials all showed a significant improvement in external quantum efficiency and a significant improvement in stability (with a reduced efficiency roll-off).

[0196] As can be seen from the above comparison, the quaternary phosphine salt compound of the present invention can effectively improve the performance of materials and devices, and the preparation cost of the quaternary phosphine salt compound is low.

[0197] Table 1. Performance comparison of OLED devices in Examples 12-22 and Comparative Examples I-II

[0198]

[0199] The compounds from Examples 1 and 5 (compound 1 [PF6] and 68 [PF6]) were doped into the host material 2,6-dicarbazole-1,5-pyridine (PYD2) thin film at a concentration of 30 wt%, and their steady-state photoluminescence spectra were tested. The results are as follows: Figure 1 As shown. By Figure 1 It is known that both compound 1 [PF6] and compound 68 [PF6] emit strong blue-green light.

[0200] The compounds from Examples 6 and 7 (compound 83[BF4] and compound 84[BF4]) were doped into the host material PYD2 thin film at a concentration of 30 wt%, and their steady-state photoluminescence spectra were tested. The results are as follows: Figure 2 As shown. By Figure 2 It is known that both compound 83 [BF4] and compound 84 [BF4] emit strong blue-green light.

[0201] Depend on Figure 3 It is known that compounds 1 [PF6], 68 [PF6], 83 [BF4], and 84 [BF4] exhibit thermally activated delayed fluorescence emission at room temperature, making them typical thermally activated delayed fluorescence materials. Moreover, their thermally activated delayed fluorescence lifetimes are relatively short (all less than 2 microseconds), which is beneficial for obtaining a smaller device efficiency roll-off.

[0202] The compounds from Examples 1 and 5 (compound 1 [PF6] and compound 68 [PF6]) were doped into the thin film of the host material PYD2 at a concentration of 30 wt%, and surface roughness was tested. The results are as follows: Figure 4 As shown. By Figure 4 It can be seen that the root mean square roughness of the film surface of compound 1 [PF6] and compound 68 [PF6] are 0.246 nm and 0.256 nm, respectively, indicating that both have excellent film-forming properties.

[0203] Thermogravimetric analysis (TGA) was performed on the compounds of Examples 1 and 5 (compound 1 [PF6] and compound 68 [PF6]), and the results are as follows: Figure 5 As shown. (From...) Figure 5 It can be seen that the thermal decomposition temperatures of compound 1 [PF6] and compound 68 [PF6] are 398℃ and 394℃, respectively, indicating that both have excellent thermal stability.

[0204] Thermogravimetric analysis (TGA) was performed on the compounds of Examples 6 and 7 (compound 83 [BF4] and compound 84 [BF4]), and the results are as follows: Figure 6 As shown, by Figure 6It can be seen that the thermal decomposition temperatures of compounds 83[BF4] and 84[BF4] are 408℃ and 397℃, respectively, indicating that both have excellent thermal stability.

[0205] The electroluminescence spectra of the organic electroluminescent devices (OLED-1 and OLED-5) of Examples 12 and 16 were tested at different driving voltages, and the results are as follows: Figure 7 As shown. By Figure 7 It can be seen that both have the same emission spectrum under different voltages, indicating that the above devices have excellent emission color stability.

[0206] The efficiency-brightness of the organic electroluminescent devices (OLED-1 and OLED-5) in Examples 12 and 16 were tested, and the results are as follows: Figure 8 As shown. By Figure 8 It can be seen that the above-mentioned device has a very high luminous efficiency.

[0207] The efficiency-brightness of the organic electroluminescent devices (OLED-6 and OLED-7) in Examples 17 and 18 were tested, and the results are as follows: Figure 9 As shown. By Figure 9 It can be seen that the above-mentioned device has a very high luminous efficiency.

[0208] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Quaternary phosphine salt derivatives represented by formula (I) or formula (II): In formula (I), X1, X2, and X3 may be the same or different, and are independently selected from the following groups: cyclohexyl, n-butyl, 13-membered heteroaryl; or, X1, X2, and X3 may be selected from unsubstituted or substituted phenyl groups with one Ra; wherein Ra is selected from acridine, dimethylacridyl, phenthiazinyl, carbazole, phenoxazinyl, or... ; X4 may be the same as or different from each other, and is independently selected from acridine, dimethylacridinyl, phenthiazinyl, carbazole, phenoxazinyl, etc. or ; n is selected from 1 or 2; In formula (II), L is selected from -phenyl-O-phenyl-; X1 and X2 are selected from phenyl; X3 is selected from phenyl substituted with one Ra; Ra is selected from acridine, dimethylacridinyl, carbazolyl, phenoxazinyl; In the two general formulas, A - The same or different, independently selected monovalent anions, the total valence of which is such that the compound is electrically neutral.

2. The quaternary phosphine salt derivative according to claim 1, characterized in that, In formula (I), X1, X2, and X3 are the same and are selected from phenyl, cyclohexyl, or n-butyl. X4 may be the same as or different from each other, and is independently selected from acridine, dimethylacridinyl, phenthiazinyl, carbazole, phenoxazinyl, etc. or ; n is selected from 1 or 2.

3. The quaternary phosphine salt derivative according to claim 1, characterized in that, In formula (I), X1 and X2 are the same and are selected from phenyl; X3 is selected from unsubstituted or phenyl groups substituted with one Ra; said Ra is selected from acridine, dimethylacridinyl, phenthiazinyl, carbazole, phenoxazinyl or... ; X4 may be the same as or different from each other, and is independently selected from acridine, dimethylacridinyl, phenthiazinyl, carbazole, phenoxazinyl, etc. or ; n is selected from 1 or 2.

4. The quaternary phosphine salt derivative according to any one of claims 1-3, characterized in that, A - The anion corresponding to the phosphonium cation in a quaternary phosphonium salt is selected from at least one of the following structures: PF6 - BF4 - , 5. Quaternary phosphine salt derivatives as shown below: ； The anion corresponding to the phosphine cation is selected from at least one of the following structures: PF6 - BF4 - , 。 6. Use of one, two, or three of the quaternary phosphine salt derivatives according to any one of claims 1-5 in the preparation of light-emitting devices.

7. The use according to claim 6, characterized in that, The light-emitting device is an organic light-emitting diode or a luminescent electrochemical cell.

8. A light-emitting device, characterized in that, It comprises two electrodes and a functional layer located between the electrodes, wherein the functional layer comprises one, two or three of the quaternary phosphine salt derivatives as described in any one of claims 1-5.

9. The light-emitting device according to claim 8, characterized in that, The functional layer is one, two, or three of the following: injection layer, transport layer, light-emitting layer, and blocking layer.

10. The light-emitting device according to claim 8, characterized in that, The quaternary phosphine salt derivative is located in the luminescent layer.

11. The light-emitting device according to claim 8, characterized in that, The light-emitting device includes a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode.

12. The method for preparing the light-emitting device according to claim 11, characterized in that, The process includes the following steps: sequentially depositing an anode, a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode on a substrate.

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