A green light iridium complex, a light-emitting material and an electroluminescent device

Abstract

This invention discloses a green iridium complex, a luminescent material, and an electroluminescent device, belonging to the field of organic light-emitting materials technology. In the green iridium complex shown in Formula I, n is selected from integers 1 to 3; q and p are independently selected from 0, 1, or 2; V1 and V2 are independently selected from one or more of carbon-carbon single bonds, -C-, -N-, -O-, and -S-; and are independently selected from one or more of substituted or unsubstituted C6-C30 aryl and C3-C30 heteroaryl groups; B1 and B2 are independently selected from H, C6-C72 aryl, C6-C30 aromatic amino, substituted or unsubstituted C1-C10 straight-chain or branched alkyl, and substituted or unsubstituted C12-C30 nitrogen-containing heteroaryl. The solubility of the green iridium complex is significantly improved, and the thin films prepared from it as luminescent materials exhibit excellent stability. The luminous efficiency and lifespan of the electroluminescent devices prepared from the thin films are significantly improved. Formula I

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting materials technology, and in particular to a green iridium complex, a light-emitting material, and an electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) possess advantages such as rich colors, thinness, wide viewing angles, fast response speeds, and the ability to fabricate flexible devices, making them one of the most promising next-generation flat panel display and solid-state lighting technologies. Currently, OLED devices have achieved large-scale applications in smartphones, wearable displays, television displays, and flexible displays, and continue to evolve towards higher resolution, higher brightness, and longer lifespan.

[0003] A typical OLED device usually consists of a multilayer structure including a transparent conductive oxide anode (such as ITO), a hole transport layer (HTL), an emissive layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), and a metal cathode. In specific device designs, some organic functional layers can be omitted or combined depending on material properties and device requirements. When an external voltage is applied across the device, holes and electrons are injected into the organic functional layers from the anode and cathode, respectively, recombine in the emissive layer to form excitons. The excitons release energy through radiative transitions as they return from the excited state to the ground state, thus achieving electroluminescence.

[0004] However, limited by the statistical laws of spin quantum luminescence, traditional fluorescent materials can only effectively utilize about 25% of singlet excitons during electroluminescence, while the remaining approximately 75% of triplet excitons are typically deactivated through non-radiative transitions, theoretically limiting the device's internal quantum efficiency (IQE) to 25%. In contrast, phosphorescent metal complexes, due to the introduction of heavy metal atoms, possess strong spin-orbit coupling that promotes intersystem crossing between singlet and triplet states, thereby achieving effective utilization of triplet excitons. Theoretically, the internal quantum efficiency of the device can reach 100%, making it of significant application value in high-efficiency OLED devices.

[0005] Among red, green, and blue phosphorescent materials, green phosphorescent iridium complexes have achieved commercial application first due to their high luminous efficiency, relatively mature energy level matching, and good device stability, becoming one of the core luminescent materials in current high-end AMOLED display panels. However, as devices develop towards higher brightness, longer lifespan, and larger area fabrication, existing green phosphorescent iridium complex materials still exhibit problems such as limited solubility, insufficient film morphology stability, and susceptibility to molecular aggregation and efficiency roll-off under high doping or high current density conditions. First, the limited solubility of these materials makes them difficult to adapt to low-cost, large-area solution processing techniques. Second, existing materials exhibit insufficient film morphology stability during film formation, especially at high doping concentrations or high current densities, where molecules are prone to excessive aggregation, leading to severe efficiency roll-off, which directly weakens the luminescent performance of the device in actual operation. In addition, the poor stability of traditional materials under long-term operation means that the device's lifespan (e.g., T95 index) cannot meet the higher standards of display requirements.

[0006] Therefore, although green phosphorescent iridium complexes have been used in commercial devices, how to further improve the processing performance, morphological stability and device lifespan of materials while maintaining their high luminous efficiency through reasonable molecular structure design remains an important technical problem that restricts their performance improvement and application expansion.

[0007] Therefore, researching and developing a novel green phosphorescent iridium complex is of great significance for electroluminescent devices. Summary of the Invention

[0008] In view of this, the technical problem to be solved by the present invention is to provide a green iridium complex, a luminescent material, and an electroluminescent device. The green iridium complex has a unique structure and excellent solubility, film-forming properties, and ease of processing. Electroluminescent devices prepared using this complex exhibit significantly improved luminous efficiency, operational stability, and lifespan.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] This invention provides a green iridium complex of Formula I:

[0011]

[0012] Formula I;

[0013] This invention introduces a conjugated solubilizing structure on the periphery of the green iridium complex molecule through rational molecular structure design. The conjugated solubilizing structure described above differs from simple alkyl chain solubilization. While improving processing performance, it can regulate energy level matching through the conjugated system, thereby maintaining or even enhancing the photoelectric performance of the material. Furthermore, this invention combines the introduction of the aforementioned conjugated solubilizing structure with the combined design of n, V1, and V2 to achieve precise control over the molecular solubility and electronic properties.

[0014] Furthermore, the present invention through the application of... , The structural constraints of B1 and B2 enable the adjustment of the steric hindrance effect and charge distribution of the green iridium complex structure, thereby finely controlling the intermolecular interaction forces, better suppressing aggregation, and optimizing the stability of the thin film prepared from the green iridium complex. Here, n is selected from an integer between 1 and 3; preferably 1.

[0015] m1 to m7 are independently selected from integers between 0 and 4; q and p are independently selected from 0, 1, or 2;

[0016] When q is 2, B1 can be two identical or different structures;

[0017] When p is 2, B2 can be two identical or different structures.

[0018] V1 and V2 are independently selected from one or more of the following: carbon-carbon single bond, -C-, -N-, -O-, -S-.

[0019] When V1 is selected from carbon-carbon single bond, -O- or -S-, there is no B1 ring in Equation I;

[0020] When V2 is selected from carbon-carbon single bond, -O- or -S-, there is no B2 ring in Equation I;

[0021] When V1 is selected from -C-, q is 2; when V1 is selected from -N-, q is 1.

[0022] When V2 is selected from -C-, p is 2; when V2 is selected from -N-, p is 1.

[0023] R 1 ~R 7 It is independently selected from one or more of the following: H, D, -CN, -NO2, -CF3, -OH, -SH, -NH2, halogen, substituted or unsubstituted C1-C30 straight-chain or branched hydrocarbon group, C3-C30 cycloalkyl group, C1-C30 alkoxy group, C1-C30 alkylthio group, C6-C60 aryl group, C6-C60 aryl ether group, C5-C60 heteroaryl group, and C5-C60 heteroaryl ether group;

[0024] , It is independently selected from one or more of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups;

[0025] B1 and B2 are independently selected from H, aryl groups of C6 to C72, aryl amino groups of C6 to C30, substituted or unsubstituted straight-chain or branched alkyl groups of C1 to C10, and substituted or unsubstituted nitrogen-containing heteroaryl groups of C12 to C30.

[0026] In formula I, R 5 The phenyl group and R 4 The phenyl group can be substituted at the ortho, meta, or para position.

[0027] In formula I, R 3 The pyridyl group and It can be used to replace adjacent, intermediate, or opposite positions.

[0028] The green iridium complex described in this invention exhibits significantly improved solubility in commonly used organic solvents, making it suitable for efficient solution preparation processes such as spin coating and inkjet printing. This not only reduces the manufacturing cost of the device but also enables the production of large-area, flexible display devices.

[0029] The green iridium complex described in this invention, through a rational molecular structure design, effectively regulates intermolecular interactions, suppressing excessive aggregation (disordered aggregation) of its molecules during the film formation and operation of electroluminescent devices. This directly optimizes the morphological stability of the thin film, physically mitigating efficiency roll-off (efficiency loss) at high current densities, allowing the device to maintain high efficiency even at high brightness. Furthermore, the luminous efficiency and lifespan of the electroluminescent device are significantly improved.

[0030] In Formula I, the C1-C30 straight-chain or branched hydrocarbon groups include straight-chain or branched alkyl, alkenyl, and alkynyl groups, specifically including, but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, ... Hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, triacontyl; vinyl, propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-decenyl, oleyl; ethynyl, propynyl, propynyl, 1-butynyl, 2-butynyl, etc.

[0031] In Formula I, the C3 to C30 cycloalkyl groups include monocyclic, bridged, fused, and spirocyclic cycloalkyl groups, specifically including but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclopentadecanyl, cyclooctadecyl; adamantyl, norbornyl, bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl; spiro[4.5]decyl, spiro[5.5]undecyl, etc.

[0032] In the structure of Formula I, the alkoxy groups of C1 to C30 specifically include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, undecoxy, dodecoxy, tetradecoxy, hexadecoxy, octadecoxy, eicosoxy, docosoxy, triadecoxy, etc.

[0033] In the structure of Formula I, the C1 to C30 alkylthio groups specifically include, but are not limited to: methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, isopentylthio, neopentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, dodecylthio, tetradecylthio, hexadecylthio, octadecylthio, eicosylthio, triacontylthio, etc.

[0034] In Formula I, the aryl groups of C6 to C60 are monocyclic or fused-ring aromatic hydrocarbon groups, specifically including but not limited to: phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 9-phenanthyl, 1-pyrene, 2-pyrene, perylene, 2-biphenyl, 3-biphenyl, 4-biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, 9-fluorenyl, etc.

[0035] In the structure of Formula I, the aryl ether groups of C6 to C60 specifically include, but are not limited to: phenoxy, 1-naphthoxy, 2-naphthoxy, 9-anthraoxy, 1-phenanthoxy, 9-phenanthoxy, 1-pyreneoxy, 2-biphenoxy, 4-biphenoxy, p-terphenyloxy, 9-fluorenoxy, etc.

[0036] In the structure of Formula I, the heteroaryl groups of C5 to C60 specifically include, but are not limited to: 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolinyl, 3-quinolinyl, 4-quinolinyl, 1-isoquinolinyl, 3-isoquinolinyl, 1-indolyl, 2-indolyl, 3-indolyl, N-carbazolyl, 2-carbazolyl, 3-carbazolyl, 2-benzofuranyl, 3-benzofuranyl, 2-benzothiophenyl, 3-benzothiophenyl, 2-benzimidazolyl, benzoxazol-2-yl, benzothiazol-2-yl, 6-purinyl, 2-quinoxolinyl, 2-quinazolinyl, 1-phthalazinyl, 1,10-phenanthroline-2-yl, 9-acridyl, phenazin-1-yl, phenthiazin-2-yl, phenoxazin-2-yl, etc.

[0037] In the structure of Formula I, the C5 to C60 heteroaryl ether groups specifically include, but are not limited to: 2-pyridinoxy, 3-pyridinoxy, 4-pyridinoxy, 2-quinolinoxy, 3-quinolinoxy, 1-isoquinolinoxy, 2-indoloxy, N-carbazoleoxy, 2-benzofuranoxy, 2-benzothiophenoxy, 2-benzimidazoloxy, 6-purineoxy, 2-quinoxalinoxy, etc.

[0038] Preferably, in this invention, the heteroatoms in the C5-C60 heteroaromatic or C5-C60 heteroaryl ether groups are independently selected from one or more of Si, Ge, N, P, O, S, and Se; more preferably, they are N, O, or S. The substituents of the C1-C30 straight-chain or branched hydrocarbon groups are selected from one or more of D, halogen, nitro, amino, and hydroxyl groups.

[0039] The substituents of the C6-C30 aryl group or the C3-C30 heteroaryl group are independently selected from one or more of the following: C1-C10 straight-chain or branched alkyl groups, C1-C6 alkoxy groups, halogen groups, amino groups, and nitro groups.

[0040] The substituents of the C1-C10 straight-chain or branched alkyl groups are selected from one or more of the aryl, halogen, amino, and nitro groups of C6-C12.

[0041] The substituents of the nitrogen-containing heteroaryl group of C12 to C30 are selected from one or more of the following: heteroaryl group of C4 to C15, straight-chain or branched alkyl group of C1 to C10, alkoxy group of C1 to C6, halogen, amino group, and nitro group.

[0042] Preferred of the present invention, , Independently selected from any of the structures shown in formulas A-1 to A-12:

[0043] .

[0044] Preferably, in this invention, B1 and B2 are independently selected from one or more of H, phenyl, biphenyl, terphenyl, polyphenyl, substituted or unsubstituted N-arylcarbazolyl, substituted or unsubstituted triphenylamine, and diphenylmethyl.

[0045] Preferably, the number of phenyl groups in the polyphenyl group is selected from an integer between 4 and 12; more preferably, it is 5, 7, or 11.

[0046] Preferably, the substituents of the triphenylamine are selected from one or more of diphenylamino, halogen, nitro, and amino; more preferably, they are diphenylamino.

[0047] Preferably, in this invention, the aryl group in the N-arylcarbazolyl group is selected from substituted or unsubstituted phenyl groups;

[0048] Preferably, the substituent of the phenyl group is selected from carbazolyl or carbazolyl-substituted carbazolyl;

[0049] More preferably, the number of substituent carbazoyl groups in the carbazoyl-substituted carbazoyl group is 1 or 2;

[0050] Preferably, the substituent of the N-arylcarbazolyl group is selected from carbazolyl groups, and the number of carbazolyl groups is 1 or 2.

[0051] Preferably, in this invention, B1 and B2 are independently selected from any of the structures shown in formulas B-1 to B-27:

[0052] .

[0053] In a further preferred embodiment of the present invention, the green iridium complex is selected from formula I. a ~I e Any of the structures shown:

[0054] Formula I a ;

[0055] Formula I b ;

[0056] Formula I c ;

[0057] Formula I d ;

[0058] Formula I e .

[0059] Wherein, n, m1~m7, R 1 ~R 7 , , The range of values ​​for B1 and B2 is the same as described above, and will not be repeated here.

[0060] In a further preferred embodiment of the present invention, the green iridium complex is selected from any of the structures shown in Formula I-1 to Formula I-69:

[0061]

[0062]

[0063] .

[0064] The present invention also provides a luminescent material comprising the above-described green iridium complex.

[0065] The green iridium complex described in this invention can be used directly as an organic light-emitting layer or mixed with other materials to form an organic light-emitting layer.

[0066] Preferably, the luminescent material further includes 8CzTPS (which is a dendritic body composed of a tetraphenylsilane core and peripheral dendritic groups 3,9'-bicarbazole).

[0067] The 8CzTPS structure is shown below:

[0068] .

[0069] More preferably, the mass ratio of the 8CzTPS to the green iridium complex is 1:(8~10); even more preferably, it is 1:9.

[0070] The present invention also provides an electroluminescent device comprising the above-described luminescent material.

[0071] Using the above-mentioned luminescent materials as organic light-emitting layers in electroluminescent devices can significantly improve the luminous efficiency, lifespan, and performance stability of the devices.

[0072] The present invention does not impose any special limitations on the structure of the organic electroluminescent device; any conventional organic electroluminescent device known to those skilled in the art is acceptable. The device can be selected and adjusted according to the application, quality requirements, and product requirements.

[0073] The preferred structure of the organic electroluminescent device of the present invention includes:

[0074] Substrate;

[0075] An anode disposed on the substrate;

[0076] An organic thin film layer (including the aforementioned organic light-emitting layer) is disposed on the anode.

[0077] The cathode is disposed on the organic thin film layer.

[0078] The organic thin film layer may be one or more layers, and at least one layer may be the organic light-emitting layer described in this invention.

[0079] The thickness of the substrate is preferably 0.3~0.7 mm, more preferably 0.4~0.6 mm;

[0080] The present invention does not have any particular limitation on the selection of the substrate. It can be any substrate of conventional organic electroluminescent devices that is well known to those skilled in the art. The selection and adjustment can be made according to the application, quality requirements and product requirements.

[0081] In this invention, the substrate is preferably glass or plastic.

[0082] In this invention, the anode can be a material that is easy to inject holes. In some specific embodiments of this invention, a conductive metal or a conductive metal oxide is preferred, and indium tin oxide is even more preferred.

[0083] In this invention, the cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum and silver, with aluminum being the most preferred.

[0084] In order to improve the performance and efficiency of light-emitting electroluminescent devices, the organic thin film layer, in addition to the light-emitting layer, preferably includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer.

[0085] The organic thin film layer between the light-emitting layer and the cathode preferably further includes one or more of a hole-blocking layer, an electron injection layer, and an electron transport layer.

[0086] The present invention does not impose any particular limitation on the materials and thicknesses of the hole injection layer, hole transport layer, electron blocking layer, organic electroluminescent layer, hole blocking layer, electron injection layer and electron transport layer, and the materials and thicknesses can be selected and adjusted according to those known to those skilled in the art.

[0087] The present invention does not impose any particular limitation on the preparation process of the electrode, hole injection layer, hole transport layer, electron blocking layer, organic electroluminescent layer, hole blocking layer, electron injection layer and electron transport layer, but preferably adopts processes such as vacuum evaporation, solution spin coating, solution scraping, inkjet printing, offset printing and stereolithography.

[0088] The present invention does not impose any particular limitation on the preparation method of the organic electroluminescent device, and is applicable to a variety of preparation processes. Specifically, it can be carried out according to the following methods or other commonly used methods:

[0089] (1) An anode is formed on the substrate;

[0090] (2) One or more organic thin film layers are formed on the anode, including at least one organic light-emitting layer;

[0091] (3) A cathode is formed on the organic thin film layer;

[0092] The organic light-emitting layer includes one or more green iridium complexes as described in this invention.

[0093] The structure and materials of the organic electroluminescent device in the above preparation method, as well as the corresponding selection principles, are the same as the materials, structures, and selection principles of the aforementioned organic electroluminescent device, and will not be repeated here.

[0094] Furthermore, the present invention does not impose any particular limitation on the method of forming the anode; any method known to those skilled in the art can be used.

[0095] The present invention does not have a particular limitation on the formation method of the organic thin film layer, which can be formed on the anode surface by means of vacuum evaporation, solution spin coating, solution scraping, inkjet printing, offset printing or stereolithography.

[0096] After the organic light-emitting layer is formed, a cathode is prepared on its surface.

[0097] The present invention does not have any particular limitation on the cathode formation method, and any method known to those skilled in the art is acceptable, including but not limited to solution processing, vacuum deposition, etc.

[0098] Compared with the prior art, the green iridium complex of Formula I provided by the present invention, wherein n is selected from an integer between 1 and 3; m1 to m7 are independently selected from integers between 0 and 4; q and p are independently selected from 0, 1, or 2; V1 and V2 are independently selected from one or more of carbon-carbon single bonds, -C-, -N-, -O-, and -S-; R 1 ~R 7 It is independently selected from one or more of the following: H, D, -CN, -NO2, -CF3, -OH, -SH, -NH2, halogen, substituted or unsubstituted C1-C30 straight-chain or branched hydrocarbon group, C3-C30 cycloalkyl group, C1-C30 alkoxy group, C1-C30 alkylthio group, C6-C60 aryl group, C6-C60 aryl ether group, C5-C60 heteroaryl group, and C5-C60 heteroaryl ether group; , The components are independently selected from one or more of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups; B1 and B2 are independently selected from H, C6-C72 aryl groups, C6-C30 arylamine groups, substituted or unsubstituted C1-C10 straight-chain or branched alkyl groups, and substituted or unsubstituted C12-C30 nitrogen-containing heteroaryl groups. The solubility of the green iridium complex described in this invention is significantly improved, and the thin films prepared using it as luminescent materials exhibit excellent stability. The luminous efficiency and lifespan of the electroluminescent devices prepared from the thin films are significantly improved. Detailed Implementation

[0099] To further illustrate the present invention, the green iridium complex, luminescent material, and electroluminescent device provided by the present invention will be described in detail below with reference to embodiments.

[0100] Example 1

[0101] The chemical structure and synthetic route of I-1 are as follows:

[0102]

[0103] Weigh 1-1 (20.00 g, 79.7 mmol), phenylboronic acid (10.69 g, 87.7 mmol), triphenylphosphine (0.21 g, 0.80 mmol), and anhydrous potassium carbonate (22.03 g, 159.4 mmol) into a 500 mL three-necked flask. Add 200 mL of acetonitrile and 100 mL of methanol. After thoroughly degassing and purging the reaction system with argon, add palladium acetate (0.45 g, 1.99 mmol) under an argon atmosphere. Heat to 50 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 1-2 (16.87 g, yield: 86.3%). Elemental analysis and structure (C 12 H 10 (BrN): Theoretical values: C, 58.09; H, 4.06; Br, 32.20; N, 5.65; Measured values: C, 58.10; H, 4.07; Br, 32.20; N, 5.66. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 247.00; Experimental value 247.0 (M + ).

[0104] Weigh 1-2 (16.00 g, 79.7 mmol), 3-chlorophenylboronic acid (11.22 g, 71.7 mmol), and anhydrous potassium carbonate (54.08 g, 391.3 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add tetrakis(triphenylphosphine)palladium (1.51 g, 1.3 mmol) under an argon atmosphere. Heat to 90 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 1-3 (16.66 g, yield: 91.3%). Elemental analysis and structure (C 18 H 14 ClN): Theoretical values: C, 77.28; H, 5.04; Cl, ​​12.67; N, 5.01; Measured values: C, 77.30; H, 5.05; Cl, ​​12.66; N, 5.00. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 279.08; Experimental value 279.1 (M + ).

[0105] Weigh 1-3 (15.00 g, 53.6 mmol), pinacol diboronate (20.42 g, 80.4 mmol), and anhydrous potassium acetate (10.52 g, 107.23 mmol) into a 250 mL three-necked flask. Add 120 mL of 1,4-dioxane and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.98 g, 1.07 mmol) and XPhos (1.02 g, 2.14 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 1-4 (16.64 g, yield: 83.6%). Elemental analysis and structure (C 24 H 26 BNO2): Theoretical values: C, 77.64; H, 7.06; B, 2.91; N, 3.77; O, 8.62; Measured values: C, 77.65; H, 7.06; B, 2.90; N, 3.78; O, 8.63. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 371.21; Experimental value 371.2 (M + ).

[0106] Weigh out 1-5 (50.00 g, 160.8 mmol), o-nitrophenylboronic acid (32.21 g, 193.0 mmol), and anhydrous potassium carbonate (44.45 g, 321.6 mmol) into a 500 mL three-necked flask. Add 200 mL of toluene. After thoroughly degassing and purging the reaction system with argon, add palladium acetate (0.72 g, 3.2 mmol) under an argon atmosphere. Heat to 60 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 1-6 (39.38 g, yield: 80.0%). Elemental analysis and structure (C 14 H 12 BrNO2): Theoretical values: C, 54.92; H, 3.95; Br, 26.10; N, 4.58; O, 10.45; Measured values: C, 54.93; H, 3.96; Br, 26.09; N, 4.57; O, 10.44. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 305.01; Experimental value 305.0 (M + ).

[0107] Weigh 1-6 (15.00 g, 49.0 mmol) and triphenylphosphine (32.14 g, 122.5 mmol) into a 100 mL three-necked flask, add 60 mL of o-dichlorobenzene (o-DCB), and dissolve the starting materials by magnetic stirring. After thorough degassing and argon purging, the mixture is heated to 220 °C and stirred for 18 hours. After the reaction is complete, cool to room temperature, and separate by column chromatography to obtain product 1-7 (10.18 g, yield: 75.8%). Elemental analysis (C...) 14 H 12 (BrN): Theoretical values: C, 61.33; H, 4.41; Br, 29.14; N, 5.11; Measured values: C, 61.33; H, 4.40; Br, 29.15; N, 5.12. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 273.02; Experimental value 273.0 (M + ).

[0108] Weigh out 1-7 (10.00 g, 36.5 mmol), cuprous iodide (1.39 g, 7.3 mmol), and anhydrous potassium carbonate (10.09 g, 73.0 mmol) into a 50 mL reaction flask. Add 20 mL of iodobenzene as a solvent and also as a reactant. Stir to dissolve the solids. After thoroughly degassing the reaction system and purging with argon, heat the reaction mixture to 180 °C and stir for 18 hours. After the reaction is complete, cool to room temperature, separate by column chromatography, and recrystallize from n-hexane to give product 1-8 (12.14 g, yield: 95.0%). Elemental analysis structure (C 20 H 16 BrN): Theoretical values: C, 68.57; H, 4.60; Br, 22.81; N, 4.00; Measured values: C, 68.58; H, 4.61; Br, 22.80; N, 3.99. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 350.26; Experimental value 350.3 (M + ).

[0109] Weigh 1-8 (6.32 g, 18.0 mmol), 1-4 (8.02 g, 21.6 mmol), and anhydrous potassium carbonate (7.46 g, 54.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.33 g, 0.36 mmol) and XPhos (0.34 g, 0.72 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 1-9 (8.49 g, yield: 91.7%). Elemental analysis and structure (C 38 H 30 N2): Theoretical values: C, 88.68; H, 5.88; N, 5.44; Measured values: C, 88.69; H, 5.89; N, 5.43. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 514.24; Experimental value 514.3 (M + )

[0110] Under an argon atmosphere, ligand 1-10 (4.66 g, 30 mmol), iridium trichloride trihydrate (3.53 g, 10 mmol), 90 mL of ethylene glycol monoethyl ether, and 30 mL of water were added to a 250 mL round-bottom flask. The mixture was heated to reflux and reacted for 24 hours. The reaction mixture was cooled to room temperature, and water was added to precipitate the product. The precipitate was filtered, washed with distilled water, and dried under vacuum to obtain product 1-11 (4.92 g, 91.79% yield).

[0111] In a 250 mL three-necked flask, phenylpyridine iridium chloride bridging ligand 1-11 (5.36 g, 5 mmol) was added, followed by 100 mL of dichloromethane, and stirred to dissolve. Silver trifluoromethanesulfonate (2.83 g, 11 mmol) was dissolved in 27 mL of isopropanol and added dropwise to the reaction system. The mixture was stirred at 25 °C for 24 hours. The reaction solution was passed through a silica gel funnel, washed with dichloromethane, and the resulting liquid was collected. The liquid was concentrated by rotary evaporation to obtain a solid, which was then dried in a vacuum oven to give a yellow solid 1-12 (7.06 g, 99.02% yield).

[0112] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, followed by sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 1-9 (7.72 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, separated by column chromatography, and recrystallized to give product I-1 (2.70 g, yield: 53.2%). Elemental analysis of the structure (C...) 60 H 45 (IrN4): Theoretical values: C, 71.05; H, 4.47; Ir, 18.95; N, 5.52; Measured values: C, 71.06; H, 4.48; Ir, 18.94; N, 5.51. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 10¹⁴.33; Experimental value 10¹⁴.3 (M⁺).

[0113] Example 2

[0114] The chemical structure and synthetic route of I-4 are as follows:

[0115]

[0116] Weigh 2-1 (50.00 g, 160.8 mmol), o-nitrophenylboronic acid (32.21 g, 193.0 mmol), and anhydrous potassium carbonate (44.45 g, 321.6 mmol) into a 500 mL three-necked flask. Add 200 mL of toluene. After thoroughly degassing and purging the reaction system with argon, add palladium acetate (0.72 g, 3.2 mmol) under an argon atmosphere. Heat to 60 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 2-2 (39.38 g, yield: 80.0%). Elemental analysis and structure (C 14 H 12 BrNO2): Theoretical values: C, 54.92; H, 3.95; Br, 26.10; N, 4.58; O, 10.45; Measured values: C, 54.93; H, 3.96; Br, 26.09; N, 4.57; O, 10.44. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 305.01; Experimental value 305.0 (M + ).

[0117] 2-2 (15.00 g, 49.0 mmol) and triphenylphosphine (32.14 g, 122.5 mmol) were weighed into a 100 mL three-necked flask. 60 mL of o-dichlorobenzene (o-DCB) was added, and the reactants were dissolved by magnetic stirring. After thorough degassing and argon purging, the mixture was heated to 220 °C and stirred for 18 hours. After the reaction was complete, the mixture was cooled to room temperature, and column chromatography was used to separate product 2-3 (10.18 g, yield: 75.8%). Elemental analysis of the structure (C...) 14 H 12 (BrN): Theoretical values: C, 61.33; H, 4.41; Br, 29.14; N, 5.11; Measured values: C, 61.33; H, 4.40; Br, 29.15; N, 5.12. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 273.02; Experimental value 273.0 (M + ).

[0118] Weigh 2-3 (10.00 g, 36.5 mmol), cuprous iodide (1.39 g, 7.3 mmol), and anhydrous potassium carbonate (10.09 g, 73.0 mmol) into a 50 mL reaction flask. Add 20 mL of iodobenzene as a solvent and also as a reactant. Stir to dissolve the solids. After thoroughly degassing the reaction system and purging with argon, heat the reaction mixture to 180 °C and stir for 18 hours. After the reaction is complete, cool to room temperature, separate by column chromatography, and recrystallize from n-hexane to give product 2-4 (12.14 g, yield: 95.0%). Elemental analysis and structure (C...) 20 H 16 (BrN): Theoretical values: C, 68.57; H, 4.60; Br, 22.81; N, 4.00; Measured values: C, 68.58; H, 4.61; Br, 22.80; N, 3.99. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 350.26; Experimental value 350.3 (M+).

[0119] Weigh 2-4 (6.32 g, 18.0 mmol), 1-4 (8.02 g, 21.6 mmol), and anhydrous potassium carbonate (7.46 g, 54.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.33 g, 0.36 mmol) and XPhos (0.34 g, 0.72 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 2-5 (8.49 g, yield: 91.7%). Elemental analysis and structure (C 38 H 30 N2): Theoretical values: C, 88.68; H, 5.88; N, 5.44; Measured values: C, 88.69; H, 5.89; N, 5.43. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 514.24; Experimental value 514.3 (M + )

[0120] Under an argon atmosphere, 90 mL of ethanol, sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 2-5 (7.72 g, 15 mmol) were added to a 250 mL three-necked flask. The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-4 (2.70 g, yield: 53.2%). 元素分析结构 (C) 60 H 45 (IrN4): Theoretical values: C, 71.05; H, 4.47; Ir, 18.95; N, 5.52; Measured values: C, 71.06; H, 4.48; Ir, 18.94; N, 5.51. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 10¹⁴.33; Experimental value 10¹⁴.3 (M⁺).

[0121] Example 3

[0122] The chemical structure and synthetic route of I-7 are as follows:

[0123]

[0124] In a 250 mL three-necked flask, 1-7 (6.32 g, 23.0 mmol), 1-4 (10.27 g, 27.7 mmol), and anhydrous potassium carbonate (9.56 g, 69.16 mmol) were weighed. 120 mL of toluene and 40 mL of ethanol were added, and the reactants were dissolved by magnetic stirring. After thorough degassing and argon purging, Pd₂(dba)₃ (0.26 g, 0.46 mmol) and XPhos (0.44 g, 0.92 mmol) were added under an argon atmosphere. The mixture was heated to 95 °C and refluxed for 10 hours. After the reaction was complete, the mixture was cooled to room temperature, the solid was filtered, and the solid was extracted with water and ethyl acetate. The organic phase was separated, dried over anhydrous sodium sulfate, and concentrated by column chromatography to obtain product 3-1 (9.27 g, yield: 91.7%). Elemental analysis of the structure (C) was performed. 32 H 26 N2): Theoretical values: C, 87.64; H, 5.98; N, 6.39; Measured values: C, 87.65; H, 5.99; N, 6.40. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 438.21; Experimental value 438.2 (M + ).

[0125] Weigh 3-1 (6.00 g, 11.7 mmol), 3-2 (4.33 g, 14.0 mmol), and sodium tert-butoxide (3.36 g, 35.0 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.53 g, 0.58 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.82 g, 1.75 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 3-3 (7.38 g, yield: 94.6%). 元素分析结构 (C) 50 H 38 N2): Theoretical values: C, 90.06; H, 5.74; N, 4.20; Measured values: C, 90.07; H, 5.75; N, 4.19. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 666.30; Experimental value 666.3 (M + ).

[0126] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 3-3 (10.00 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-7 (3.12 g, yield: 53.5%). Elemental analysis of the structure (C...) 72 H 53 IrN4): Theoretical values: C, 74.14; H, 4.58; Ir, 16.48; N, 4.80; Measured values: C, 74.15; H, 4.59; Ir, 16.47; N, 4.79. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) theoretical value: 1166.39; Experimental value: 1166.4 (M + ).

[0127] Example 4

[0128] The chemical structure and synthetic route of I-10 are as follows:

[0129]

[0130] Weigh 4-1 (20.00 g, 48.924 mmol), 2-biphenylboronic acid (24.221 g, 122.3 mmol), and anhydrous potassium carbonate (16.904 g, 122.3 mmol) into a 500 mL two-necked flask. Add 200 mL of tetrahydrofuran and 80 mL of water. After thoroughly degassing the reaction system and purging with argon, add tetratetraphenylphosphine palladium (1.696 g, 1.468 mmol) under an argon atmosphere. Heat to 70 °C under argon protection and reflux with stirring for 24 hours. After the reaction is complete, cool to room temperature, wash the tetrahydrofuran and inorganic salts with water, extract with ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, recrystallize with methanol, wash with methanol, filter, and dry under vacuum to obtain product 4-2 (20.01 g, yield: 88.6%). 元素分析结构 (C) 30 H 21 Br): Theoretical values: C, 78.09; H, 4.59; Br, 17.32; Measured values: C, 78.10; H, 4.60; Br, 17.31. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 460.08; Experimental value 460.1 (M + ).

[0131] Weigh 3-1 (6.00 g, 13.7 mmol), 4-2 (7.58 g, 16.4 mmol), and sodium tert-butoxide (3.36 g, 35.0 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.53 g, 0.58 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.82 g, 1.75 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 4-3 (10.62 g, yield: 94.6%). Elemental analysis and structure (C 62 H 46 N2): Theoretical values: C, 90.92; H, 5.66; N, 3.42; Measured values: C, 90.93; H, 5.67; N, 3.41. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 818.37; Experimental value 818.4 (M + ).

[0132] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 4-3 (12.29 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-10 (3.53 g, yield: 53.5%). Elemental analysis of the structure (C...) 84 H 61 IrN4): Theoretical values: C, 76.51; H, 4.66; Ir, 14.58; N, 4.25; Measured values: C, 76.52; H, 4.67; Ir, 14.57; N, 4.24. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1318.45; Experimental value 1318.5 (M + ).

[0133] Example 5

[0134] The chemical structure and synthetic route of I-13 are as follows:

[0135]

[0136] Weigh 3-1 (6.00 g, 13.7 mmol), 5-1 (7.59 g, 16.4 mmol), and sodium tert-butoxide (3.36 g, 35.0 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.53 g, 0.58 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.82 g, 1.75 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 5-2 (8.62 g, yield: 94.6%). 元素分析结构 (C) 50 H 38 N2): Theoretical values: C, 90.06; H, 5.74; N, 4.20; Measured values: C, 90.07; H, 5.75; N, 4.19. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 666.30; Experimental value 666.3 (M+).

[0137] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 5-2 (10.00 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-13 (3.12 g, yield: 53.5%). Elemental analysis of the structure (C...) 72 H 53 (IrN4): Theoretical values: C, 74.14; H, 4.58; Ir, 16.48; N, 4.80; Measured values: C, 74.15; H, 4.59; Ir, 16.47; N, 4.79. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1166.39; Experimental value 1166.4 (M+).

[0138] Example 6

[0139] The chemical structure and synthetic route of I-16 are as follows:

[0140]

[0141] Weigh 6-2 (20.00 g, 74.8 mmol), 6-1 (31.98 g, 89.8 mmol), and anhydrous potassium carbonate (31.01 g, 224.4 mmol) into a 500 mL three-necked flask. Add 200 mL of toluene and 100 mL of ethanol. After thoroughly degassing and purging the reaction system with argon, add tetrakis(triphenylphosphine)palladium (1.73 g, 1.50 mmol) under an argon atmosphere. Heat to 90 °C under argon protection and reflux with stirring for 12 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 6-3 (32.10 g, yield: 93.0%). 元素分析结构 (C) 30 H 21 (Br): Theoretical values: C, 78.09; H, 4.59; Br, 17.32; Measured values: C, 78.10; H, 4.60; Br, 17.31. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 460.08; Experimental value 460.1 (M+).

[0142] Weigh 3-1 (6.00 g, 13.7 mmol), 6-3 (7.57 g, 16.4 mmol), and sodium tert-butoxide (3.36 g, 35.0 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.53 g, 0.58 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.82 g, 1.75 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 6-4 (10.62 g, yield: 94.6%). Elemental analysis and structure (C 62 H 46 N2): Theoretical values: C, 90.92; H, 5.66; N, 3.42; Measured values: C, 90.93; H, 5.67; N, 3.41. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 818.37; Experimental value 818.4 (M+).

[0143] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 6-4 (12.29 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-16 (3.53 g, yield: 53.5%). 元素分析结构 (C) 84 H 61 (IrN4): Theoretical values: C, 76.51; H, 4.66; Ir, 14.58; N, 4.25; Measured values: C, 76.52; H, 4.67; Ir, 14.57; N, 4.24. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1318.45; Experimental value 1318.5 (M+).

[0144] Example 7

[0145] The chemical structure and synthetic route of I-19 are as follows:

[0146]

[0147] Weigh 3-1 (22.52 g, 51.4 mmol), 7-1 (20.00 g, 61.7 mmol), and sodium tert-butoxide (12.60 g, 131.1 mmol) into a 100 mL three-necked flask. Add 150 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (1.98 g, 2.16 mmol) and tri-tert-butylphosphine tetrafluoroborate (3.08 g, 6.56 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 7-2 (33.16 g, yield: 94.6%). Elemental analysis and structure (C 50 H 39 N3): Theoretical values: C, 88.07; H, 5.77; N, 6.16; Measured values: C, 88.08; H, 5.78; N, 6.15. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) theoretical value: 681.31; Experimental value: 681.3 (M+).

[0148] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 7-2 (10.23 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-19 (3.16 g, yield: 53.5%). 元素分析结构 (C) 72 H 54 (IrN5): Theoretical values: C, 73.20; H, 4.61; Ir, 16.27; N, 5.93; Measured values: C, 73.21; H, 4.62; Ir, 16.26; N, 5.92. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1181.40; Experimental value 1181.4 (M+).

[0149] Example 8

[0150] The chemical structure and synthetic route of I-22 are as follows:

[0151]

[0152] Weigh 3-1 (13.20 g, 30.1 mmol), 8-1 (14.80 g, 30.1 mmol), and sodium tert-butoxide (7.39 g, 76.9 mmol) into a 250 mL three-necked flask. Add 100 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (1.16 g, 1.27 mmol) and tri-tert-butylphosphine tetrafluoroborate (1.80 g, 3.83 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 8-2 (24.20 g, yield: 94.6%). 元素分析结构 (C) 62 H 48 N4): Theoretical values: C, 87.70; H, 5.70; N, 6.60; Measured values: C, 87.71; H, 5.71; N, 6.59. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 848.39; Experimental value 848.4 (M+).

[0153] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 8-2 (12.74 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-22 (3.61 g, yield: 53.5%). Elemental analysis of the structure (C...) 84 H 63 (IrN6): Theoretical values: C, 74.81; H, 4.71; Ir, 14.25; N, 6.23; Measured values: C, 74.82; H, 4.72; Ir, 14.24; N, 6.22. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1348.47; Experimental value 1348.5 (M+).

[0154] Example 9

[0155] The chemical structure and synthetic route of I-25 are as follows:

[0156]

[0157] Weigh 3-1 (22.70 g, 51.8 mmol), 9-1 (20.00 g, 62.1 mmol), and sodium tert-butoxide (12.60 g, 131.1 mmol) into a 250 mL three-necked flask. Add 150 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (2.00 g, 2.18 mmol) and tri-tert-butylphosphine tetrafluoroborate (3.10 g, 6.60 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 9-2 (32.70 g, yield: 93.8%). 元素分析结构 (C) 50 H 37 N3): Theoretical values: C, 88.33; H, 5.49; N, 6.18; Measured values: C, 88.34; H, 5.50; N, 6.17. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 679.30; Experimental value 679.3 (M+).

[0158] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 9-2 (10.20 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-25 (3.11 g, yield: 52.8%). Elemental analysis of the structure (C...) 72 H 52 (IrN5): Theoretical values: C, 73.32; H, 4.44; Ir, 16.30; N, 5.94; Measured values: C, 73.33; H, 4.45; Ir, 16.29; N, 5.93. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1179.39; Experimental value 1179.4 (M+).

[0159] Example 10

[0160] The chemical structure and synthetic route of I-28 are as follows:

[0161]

[0162] Weigh 22.80 g (52.0 mmol) of 3⁻¹, 20.00 g (41.0 mmol) of 10⁻¹, and 10.10 g (105.1 mmol) of sodium tert-butoxide into a 250 mL three-necked flask. Add 150 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd₂(dba)₃ (1.58 g, 1.73 mmol) and tri-tert-butylphosphine tetrafluoroborate (2.45 g, 5.22 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 10⁻² (31.82 g, yield: 92.1%). 元素分析结构 (C) 62 H 44 N4): Theoretical values: C, 88.12; H, 5.25; N, 6.63; Measured values: C, 88.13; H, 5.26; N, 6.62. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 844.36; Experimental value 844.4 (M+).

[0163] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 10-2 (12.68 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-28 (3.54 g, yield: 52.6%). Elemental analysis of the structure (C...) 84 H 59 (IrN6): Theoretical values: C, 75.03; H, 4.42; Ir, 14.29; N, 6.25; Measured values: C, 75.04; H, 4.43; Ir, 14.28; N, 6.24. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1344.44; Experimental value 1344.5 (M+).

[0164] Example 11

[0165] The chemical structure and synthetic route of I-31 are as follows:

[0166]

[0167] Weigh 2-3 (6.32 g, 23.0 mmol), 1-4 (10.27 g, 27.7 mmol), and anhydrous potassium carbonate (9.56 g, 69.16 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.26 g, 0.46 mmol) and XPhos (0.44 g, 0.92 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 11-1 (9.27 g, yield: 91.7%). 元素分析结构 (C) 32 H 26 N2): Theoretical values: C, 87.64; H, 5.98; N, 6.39; Measured values: C, 87.65; H, 5.99; N, 6.40. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 438.21; Experimental value 438.2 (M + ).

[0168] Weigh 4-1 (20.00 g, 48.924 mmol), 3-biphenylboronic acid (24.221 g, 122.3 mmol), and anhydrous potassium carbonate (16.904 g, 122.3 mmol) into a 500 mL two-necked flask. Add 200 mL of tetrahydrofuran and 80 mL of water. After thoroughly degassing the reaction system and purging with argon, add tetratetraphenylphosphine palladium (1.696 g, 1.468 mmol) under an argon atmosphere. Heat to 70 °C under argon protection and reflux with stirring for 24 hours. After the reaction is complete, cool to room temperature, wash the tetrahydrofuran and inorganic salts with water, extract with ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, recrystallize with methanol, wash with methanol, filter, and dry under vacuum to obtain product 11-2 (20.01 g, yield: 88.6%). Elemental analysis and structure (C 30 H 21 Br): Theoretical values: C, 78.09; H, 4.59; Br, 17.32; Measured values: C, 78.10; H, 4.60; Br, 17.31. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 460.08; Experimental value 460.1 (M + ).

[0169] Weigh 11-1 (6.00 g, 13.7 mmol), 11-2 (7.58 g, 16.4 mmol), and sodium tert-butoxide (3.36 g, 35.0 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.53 g, 0.58 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.82 g, 1.75 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 11-3 (10.62 g, yield: 94.6%). 元素分析结构 (C) 62 H 46 N2): Theoretical values: C, 90.92; H, 5.66; N, 3.42; Measured values: C, 90.93; H, 5.67; N, 3.41. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 818.37; Experimental value 818.4 (M + ).

[0170] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 11-3 (12.29 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-31 (3.53 g, yield: 53.5%). Elemental analysis of the structure (C...) 84 H 61 IrN4): Theoretical values: C, 76.51; H, 4.66; Ir, 14.58; N, 4.25; Measured values: C, 76.52; H, 4.67; Ir, 14.57; N, 4.24. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1318.45; Experimental value 1318.5 (M + ).

[0171] Example 12

[0172] The chemical structure and synthetic route of I-34 are as follows:

[0173]

[0174] Weigh 11-1 (6.00 g, 13.7 mmol), 4-bromo-1,1':3',1''-terphenyl (5.08 g, 16.4 mmol), and sodium tert-butoxide (3.95 g, 41.1 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.25 g, 0.27 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.32 g, 1.10 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 12-1 (8.59 g, yield: 94.0%). 元素分析结构 (C) 50 H 38 N2): Theoretical values: C, 90.06; H, 5.74; N, 4.20; Measured values: C, 90.07; H, 5.75; N, 4.19. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 666.30; Experimental value 666.3 (M+).

[0175] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 12-1 (10.00 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-34 (3.12 g, yield: 53.5%). Elemental analysis of the structure (C...) 72 H 53 (IrN4): Theoretical values: C, 74.14; H, 4.58; Ir, 16.48; N, 4.80; Measured values: C, 74.15; H, 4.59; Ir, 16.47; N, 4.79. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1166.39; Experimental value 1166.4 (M+).

[0176] Example 13

[0177] The chemical structure and synthetic route of I-37 are as follows:

[0178]

[0179] Weigh 1-2 (20.00 g, 80.6 mmol), p-chlorophenylboronic acid (11.34 g, 72.5 mmol), and anhydrous potassium carbonate (54.60 g, 395.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add tetrakis(triphenylphosphine)palladium (1.52 g, 1.32 mmol) under an argon atmosphere. Heat to 90 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 13-1 (20.59 g, yield: 91.3%). 元素分析结构 (C) 18 H 14 ClN): Theoretical values: C, 77.28; H, 5.04; Cl, ​​12.67; N, 5.01; Measured values: C, 77.30; H, 5.05; Cl, ​​12.66; N, 5.00. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 279.08; Experimental value 279.1 (M+).

[0180] Weigh 13-1 (15.00 g, 53.6 mmol), pinacol diborate (20.42 g, 80.4 mmol), and anhydrous potassium acetate (10.52 g, 107.23 mmol) into a 250 mL three-necked flask. Add 120 mL of 1,4-dioxane and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.98 g, 1.07 mmol) and XPhos (1.02 g, 2.14 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 13-2 (16.64 g, yield: 83.6%). Elemental analysis structure (C 24 H 26 BNO2): Theoretical values: C, 77.64; H, 7.06; B, 2.91; N, 3.77; O, 8.62; Measured values: C, 77.65; H, 7.06; B, 2.90; N, 3.78; O, 8.63. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 371.21; Experimental value 371.2 (M + ).

[0181] Weigh 2-3 (6.32 g, 18.0 mmol), 13-2 (8.02 g, 21.6 mmol), and anhydrous potassium carbonate (7.46 g, 54.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.33 g, 0.36 mmol) and XPhos (0.34 g, 0.72 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 13-3 (8.49 g, yield: 91.7%). 元素分析结构 (C) 38 H 30 N2): Theoretical values: C, 88.68; H, 5.88; N, 5.44; Measured values: C, 88.69; H, 5.89; N, 5.43. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 514.24; Experimental value 514.3 (M + )

[0182] Weigh 13-3 (6.00 g, 13.7 mmol), 3-bromobiphenyl (3.82 g, 16.4 mmol), and sodium tert-butoxide (3.95 g, 41.1 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.53 g, 0.58 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.82 g, 1.75 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 13-4 (7.62 g, yield: 94.2%). Elemental analysis and structure (C 44 H 34 N2): Theoretical values: C, 89.46; H, 5.80; N, 4.74; Measured values: C, 89.47; H, 5.81; N, 4.73. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 590.27; Experimental value 590.3 (M+).

[0183] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 13-4 (8.86 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-37 (2.92 g, yield: 53.5%). Elemental analysis of the structure (C...) 66 H 49 IrN4): Theoretical values: C, 72.70; H, 4.53; Ir, 17.63; N, 5.14; Measured values: C, 72.71; H, 4.54; Ir, 17.62; N, 5.13. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1090.36; Experimental value 1090.4 (M+). Example 14

[0184] The chemical structure and synthetic route of I-40 are as follows:

[0185]

[0186] Weigh 1-7 (6.32 g, 18.0 mmol), 13-2 (8.02 g, 21.6 mmol), and anhydrous potassium carbonate (7.46 g, 54.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.33 g, 0.36 mmol) and XPhos (0.34 g, 0.72 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 14-1 (8.49 g, yield: 91.7%). 元素分析结构 (C) 38 H 30 N2): Theoretical values: C, 88.68; H, 5.88; N, 5.44; Measured values: C, 88.69; H, 5.89; N, 5.43. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 514.24; Experimental value 514.3 (M + )

[0187] Weigh 14-1 (6.00 g, 13.7 mmol), 4-bromo-1,1':4',1''-terphenyl (5.08 g, 16.4 mmol), and sodium tert-butoxide (3.95 g, 41.1 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.25 g, 0.27 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.32 g, 1.10 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 14-2 (8.59 g, yield: 94.0%). Elemental analysis structure (C 50 H 38 N2): Theoretical values: C, 90.06; H, 5.74; N, 4.20; Measured values: C, 90.07; H, 5.75; N, 4.19. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 666.30; Experimental value 666.3 (M+).

[0188] Under an argon atmosphere, 90 mL of ethanol, sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 14-2 (10.00 g, 15 mmol) were added to a 250 mL three-necked flask. The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-40 (3.12 g, yield: 53.5%). 元素分析结构 (C) 72 H 53 (IrN4): Theoretical values: C, 74.14; H, 4.58; Ir, 16.48; N, 4.80; Measured values: C, 74.15; H, 4.59; Ir, 16.47; N, 4.79. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1166.39; Experimental value 1166.4 (M+).

[0189] Example 15

[0190] The chemical structure and synthetic route of I-43 are as follows:

[0191]

[0192] Weigh 14-1 (6.00 g, 13.7 mmol), 4-bromobiphenyl (3.83 g, 16.4 mmol), and sodium tert-butoxide (3.94 g, 41.0 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.25 g, 0.27 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.16 g, 0.55 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 15-1 (7.60 g, yield: 94.0%). Elemental analysis and structure (C 44 H 34 N2): Theoretical values: C, 89.46; H, 5.80; N, 4.74; Measured values: C, 89.47; H, 5.81; N, 4.73. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 590.27; Experimental value 590.3 (M+).

[0193] Under an argon atmosphere, 90 mL of ethanol, sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 15-1 (8.86 g, 15 mmol) were added to a 250 mL three-necked flask. The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-43 (2.92 g, yield: 53.5%). 元素分析结构 (C) 66 H 49 (IrN4): Theoretical values: C, 72.70; H, 4.53; Ir, 17.63; N, 5.14; Measured values: C, 72.71; H, 4.54; Ir, 17.62; N, 5.13. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1090.36; Experimental value 1090.4 (M+).

[0194] Example 16

[0195] The chemical structure and synthetic route of I-46 are as follows:

[0196]

[0197] Weigh 13-3 (6.00 g, 13.7 mmol), 3-bromo-1,1':4',1''-terphenyl (5.08 g, 16.4 mmol), and sodium tert-butoxide (3.95 g, 41.1 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.25 g, 0.27 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.32 g, 1.10 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 16-1 (8.41 g, yield: 94.0%). Elemental analysis structure (C 49 H 36 N2): Theoretical values: C, 90.15; H, 5.56; N, 4.29; Measured values: C, 90.16; H, 5.57; N, 4.28. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 652.29; Experimental value 652.3 (M+).

[0198] Under an argon atmosphere, 90 mL of ethanol, sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 16-1 (9.79 g, 15 mmol) were added to a 250 mL three-necked flask. The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-46 (3.08 g, yield: 53.5%). 元素分析结构 (C) 71 H 51 (IrN4): Theoretical values: C, 74.00; H, 4.46; Ir, 16.68; N, 4.86; Measured values: C, 74.01; H, 4.47; Ir, 16.67; N, 4.85. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1152.37; Experimental value 1152.4 (M+).

[0199] Example 17

[0200] The chemical structure and synthetic route of I-49 are as follows:

[0201]

[0202] Weigh 1-2 (20.00 g, 80.6 mmol), (3-chloro-2-methylphenyl)boric acid (12.35 g, 72.5 mmol), and anhydrous potassium carbonate (54.59 g, 395.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add tetrakis(triphenylphosphine)palladium (1.51 g, 1.31 mmol) under an argon atmosphere. Heat to 90 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 17-1 (21.62 g, yield: 91.3%). 元素分析结构 (C) 19 H 16 ClN): Theoretical values: C, 77.68; H, 5.49; Cl, ​​12.07; N, 4.77; Measured values: C, 77.69; H, 5.50; Cl, ​​12.06; N, 4.76. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 293.10; Experimental value 293.1 (M+).

[0203] Weigh 17-1 (20.00 g, 68.1 mmol), pinacol diborate (19.02 g, 74.9 mmol), and anhydrous potassium acetate (20.05 g, 204.3 mmol) into a 250 mL three-necked flask. Add 120 mL of 1,4-dioxane and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.62 g, 0.68 mmol) and XPhos (0.65 g, 1.36 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 17-2 (21.93 g, yield: 83.6%). Elemental analysis structure (C 25 H 28 BNO2): Theoretical values: C, 77.93; H, 7.32; B, 2.81; N, 3.64; O, 8.30; Measured values: C, 77.94; H, 7.33; B, 2.80; N, 3.63; O, 8.29. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 385.22; Experimental value 385.2 (M+).

[0204] Weigh 2-3 (6.32 g, 23.0 mmol), 17-2 (10.63 g, 27.6 mmol), and anhydrous potassium carbonate (9.54 g, 69.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.42 g, 0.46 mmol) and XPhos (0.40 g, 0.92 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 17-3 (9.55 g, yield: 91.7%). 元素分析结构 (C) 33 H 28 N2): Theoretical values: C, 87.57; H, 6.24; N, 6.19; Measured values: C, 87.58; H, 6.25; N, 6.18. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 452.23; Experimental value 452.2 (M+).

[0205] Weigh 17-3 (5.00 g, 11.05 mmol), 5''-bromo-1,1':4',1'':3'',1''':4''',1''''-pentaphenyl (6.12 g, 13.26 mmol), and sodium tert-butoxide (3.19 g, 33.15 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the raw materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.20 g, 0.22 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.26 g, 0.88 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction was complete, the mixture was cooled to room temperature, the solid was filtered, and extracted with water and ethyl acetate. The organic phase was separated, dried with anhydrous sodium sulfate, and the filtered organic phase was concentrated and separated by column chromatography to give product 17-4 (8.65 g, yield: 94.0%). Elemental analysis of the structure (C...) 63 H 48 N2): Theoretical values: C, 90.83; H, 5.81; N, 3.36; Measured values: C, 90.84; H, 5.82; N, 3.35. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 832.38; Experimental value 832.4 (M+).

[0206] Under an argon atmosphere, 90 mL of ethanol, sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 17-4 (12.50 g, 15 mmol) were added to a 250 mL three-necked flask. The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-49 (3.57 g, yield: 53.6%). 元素分析结构 (C) 85 H 63 IrN4): Theoretical values: C, 76.61; H, 4.77; Ir, 14.42; N, 4.20; Measured values: C, 76.62; H, 4.78; Ir, 14.41; N, 4.19. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1332.47; Experimental value 1332.5 (M+). Example 18

[0207] The chemical structure and synthetic route of I-52 are as follows:

[0208]

[0209] Weigh 17-3 (5.00 g, 11.05 mmol), 3-bromo-1,1':2',1''-terphenyl (4.10 g, 13.26 mmol), and sodium tert-butoxide (3.19 g, 33.15 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.20 g, 0.22 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.26 g, 0.88 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 18-1 (7.08 g, yield: 94.0%). Elemental analysis structure (C 51 H 40 N2): Theoretical values: C, 89.96; H, 5.92; N, 4.11; Measured values: C, 89.97; H, 5.93; N, 4.10. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 680.32; Experimental value 680.3 (M+).

[0210] Under an argon atmosphere, 90 mL of ethanol, sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 18-1 (10.21 g, 15 mmol) were added to a 250 mL three-necked flask. The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to give product I-52 (3.16 g, yield: 53.5%). 元素分析结构 (C) 73 H 55 (IrN4): Theoretical values: C, 74.27; H, 4.70; Ir, 16.28; N, 4.75; Measured values: C, 74.28; H, 4.71; Ir, 16.27; N, 4.74. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1180.41; Experimental value 1180.4 (M+).

[0211] Example 19

[0212] The chemical structure and synthetic route of I-55 are as follows:

[0213]

[0214] Weigh 1-7 (6.32 g, 23.0 mmol), 17-2 (10.63 g, 27.6 mmol), and anhydrous potassium carbonate (9.54 g, 69.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.42 g, 0.46 mmol) and XPhos (0.40 g, 0.92 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 19-1 (9.55 g, yield: 91.7%). Elemental analysis and structure (C 33 H 28 N2): Theoretical values: C, 87.57; H, 6.24; N, 6.19; Measured values: C, 87.58; H, 6.25; N, 6.18. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 452.23; Experimental value 452.2 (M+).

[0215] Weigh 19-1 (5.00 g, 11.05 mmol), 9-(4-bromophenyl)-9H-carbazole (4.41 g, 13.26 mmol), and sodium tert-butoxide (3.19 g, 33.15 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.20 g, 0.22 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.26 g, 0.88 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 19-2 (7.21 g, yield: 94.0%). 元素分析结构 (C) 51 H 39 N3): Theoretical values: C, 88.28; H, 5.67; N, 6.06; Measured values: C, 88.29; H, 5.68; N, 6.05. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 693.31; Experimental value 693.3 (M+).

[0216] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 19-2 (10.44 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-55 (3.20 g, yield: 53.6%). Elemental analysis of the structure (C...) 73 H 54 (IrN5): Theoretical values: C, 73.47; H, 4.56; Ir, 16.11; N, 5.87; Measured values: C, 73.48; H, 4.57; Ir, 16.10; N, 5.86. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1193.40; Experimental value 1193.4 (M+).

[0217] Example 20

[0218] The chemical structure and synthetic route of I-58 are as follows:

[0219]

[0220] Weigh 19-1 (5.00 g, 11.05 mmol), 4-bromo-N,N-diphenylaniline (4.30 g, 13.26 mmol), and sodium tert-butoxide (3.19 g, 33.15 mmol) into a 100 mL three-necked flask. Add 50 mL of toluene and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.20 g, 0.22 mmol) and tri-tert-butylphosphine tetrafluoroborate (0.13 g, 0.45 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 20-1 (7.23 g, yield: 94.0%). 元素分析结构 (C) 51 H 41 N3): Theoretical values: C, 88.02; H, 5.94; N, 6.04; Measured values: C, 88.03; H, 5.95; N, 6.03. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) theoretical value: 695.33; Experimental value: 695.3 (M+).

[0221] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 20-1 (10.44 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-58 (3.20 g, yield: 53.5%). Elemental analysis of the structure (C...) 73 H 56 (IrN5): Theoretical values: C, 73.34; H, 4.72; Ir, 16.08; N, 5.86; Measured values: C, 73.35; H, 4.73; Ir, 16.07; N, 5.85. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1195.42; Experimental value 1195.4 (M+).

[0222] Example 21

[0223] The chemical structure and synthetic route of I-61 are as follows:

[0224]

[0225] Weigh 1-2 (20.00 g, 80.6 mmol), (3-chloro-2,4-dimethylphenyl)boric acid (16.36 g, 88.7 mmol), and anhydrous potassium carbonate (22.28 g, 161.2 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add tetratetraphenylphosphine palladium (1.53 g, 1.32 mmol) under an argon atmosphere. Heat to 90 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 21-1 (22.65 g, yield: 91.3%). 元素分析结构 (C) 20 H 18 ClN): Theoretical values: C, 78.04; H, 5.89; Cl, ​​11.52; N, 4.55; Measured values: C, 78.05; H, 5.90; Cl, ​​11.51; N, 4.54. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 307.11; Experimental value 307.1 (M+).

[0226] Weigh 21-1 (20.00 g, 65.0 mmol), pinacol diborate (18.15 g, 71.5 mmol), and anhydrous potassium acetate (19.13 g, 195.0 mmol) into a 250 mL three-necked flask. Add 120 mL of 1,4-dioxane and dissolve the starting materials with magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.65 g, 0.71 mmol) and XPhos (0.62 g, 1.43 mmol) under an argon atmosphere. Heat to 110 °C under argon protection and reflux with stirring for 18 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 21-2 (21.68 g, yield: 83.6%). Elemental analysis structure (C 26 H 30 BNO2): Theoretical values: C, 78.20; H, 7.57; B, 2.71; N, 3.51; O, 8.01; Measured values: C, 78.21; H, 7.58; B, 2.70; N, 3.50; O, 8.00. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 399.24; Experimental value 399.2 (M+).

[0227] Weigh 21-3 (10.00 g, 40.5 mmol), 21-2 (19.42 g, 48.6 mmol), and anhydrous potassium carbonate (16.80 g, 121.5 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.74 g, 0.81 mmol) and XPhos (0.77 g, 1.62 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux with stirring for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 21-4 (16.19 g, yield: 91.0%). 元素分析结构 (C) 32 H 25 NO: Theoretical values: C, 87.44; H, 5.73; N, 3.19; O, 3.64; Measured values: C, 87.45; H, 5.74; N, 3.18; O, 3.63. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) theoretical value: 439.19; Experimental value: 439.2 (M+).

[0228] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 21-4 (6.59 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-61 (2.51 g, yield: 53.5%). Elemental analysis of the structure (C...) 54 H 40 (IrN3O): Theoretical values: C, 69.06; H, 4.29; Ir, 20.47; N, 4.47; O, 1.70; Measured values: C, 69.07; H, 4.30; Ir, 20.46; N, 4.46; O, 1.69. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 939.28; Experimental value 939.3 (M+).

[0229] Example 22

[0230] The chemical structure and synthetic route of I-64 are as follows:

[0231]

[0232] Weigh 21-2 (10.00 g, 25.0 mmol), 22-1 (9.45 g, 30.0 mmol), and anhydrous potassium carbonate (10.35 g, 75.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.46 g, 0.50 mmol) and XPhos (0.48 g, 1.00 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 22-2 (11.55 g, yield: 91.0%). 元素分析结构 (C) 38 H 37 N): Theoretical values: C, 89.90; H, 7.35; N, 2.76; Measured values: C, 89.91; H, 7.36; N, 2.75. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) theoretical value: 507.29; experimental value: 507.3 (M+).

[0233] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 22-2 (7.62 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-64 (2.70 g, yield: 53.6%). Elemental analysis of the structure (C...) 60 H 52 (IrN3): Theoretical values: C, 71.54; H, 5.20; Ir, 19.08; N, 4.17; Measured values: C, 71.55; H, 5.21; Ir, 19.07; N, 4.16. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1007.38; Experimental value 1007.4 (M+).

[0234] Example 23

[0235] The chemical structure and synthetic route of I-67 are as follows:

[0236]

[0237] Weigh 21-2 (10.00 g, 25.0 mmol), 23-1 (11.92 g, 30.0 mmol), and anhydrous potassium carbonate (10.35 g, 75.0 mmol) into a 250 mL three-necked flask. Add 120 mL of toluene and 40 mL of ethanol, and dissolve the starting materials by magnetic stirring. After thoroughly degassing and purging the reaction system with argon, add Pd2(dba)3 (0.46 g, 0.50 mmol) and XPhos (0.48 g, 1.00 mmol) under an argon atmosphere. Heat to 95 °C under argon protection and reflux for 10 hours. After the reaction is complete, cool to room temperature, filter the solid, extract with water and ethyl acetate, separate the organic phase, dry with anhydrous sodium sulfate, concentrate the filtered organic phase, and separate by column chromatography to obtain product 23-2 (13.41 g, yield: 91.0%). Elemental analysis and structure (C 45 H 35 N): Theoretical values: C, 91.64; H, 5.98; N, 2.37; Measured values: C, 91.65; H, 5.99; N, 2.36. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) theoretical value: 589.28; experimental value: 589.3 (M+).

[0238] Under an argon atmosphere, 90 mL of ethanol was added to a 250 mL three-necked flask, along with sulfonic acid compounds 1-12 (3.57 g, 5 mmol) and 23-2 (8.85 g, 15 mmol). The mixture was heated to 90 °C and reacted at this temperature for 15 hours. The reaction mixture was then cooled to room temperature. The mixture was filtered, recrystallized from the ethanol, filtered again, and separated by column chromatography to obtain product I-67 (2.92 g, yield: 53.6%). Elemental analysis of the structure (C...) 67 H 50 (IrN3): Theoretical values: C, 73.87; H, 4.63; Ir, 17.64; N, 3.86; Measured values: C, 73.88; H, 4.64; Ir, 17.63; N, 3.85. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS): Theoretical value 1089.36; Experimental value 1089.4 (M+).

[0239] Solubility and Device Examples: Examples 24-46

[0240] This invention provides a device structure for fabricating organic electroluminescent devices:

[0241] The device structure is as follows: ITO / PEDOT:PSS (50 nm) / PVK (15 nm) / organic light-emitting layer (a blend of the green iridium complex described in this invention and the host material 8CzTPS (mass ratio 1:9) (30 nm)) / mSiTRZ (12 nm) / TmPPPyTz (55 nm) / LiF (1 nm) / Al (150 nm). (This is the device structure of Examples 24-46 below, the difference being that the green iridium complex structure is different in each example.)

[0242] The device fabrication steps are as follows: Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) is spin-coated onto indium tin oxide (ITO) supported on a glass substrate and annealed at 120°C for 60 minutes. Then, a solution of o-dichlorobenzene containing poly(9-ethylenecarbazole) (PVK) is spin-coated at 2000 rpm and annealed at 100°C for 30 minutes. Next, a chlorobenzene solution containing the invented green iridium complex with a conjugated solubilizing structure and 8CzTPS mixed at a mass ratio of 1:9 is spin-coated at 1500 rpm for 1 minute and annealed at 100°C for 30 minutes. Finally, the device is fabricated at 4×10⁻⁶ rpm. -5 An organic electroluminescent device was obtained by sequentially depositing mSiTRZ, TmPPPyTz, and a LiF / Al cathode under a vacuum of Pa, where mSiTRZ and TmPPPyTz serve as the hole blocking layer and electron transport layer, respectively. The structural formula is shown below:

[0243]

[0244] Example 24

[0245] Using I-1 from Example 1 as the implementation object, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0246] Example 25

[0247] Using I-4 from Example 2 as the implementation object, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0248] Example 26

[0249] Using I-7 from Example 3 as the implementation object, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0250] Example 27

[0251] Using I-10 from Example 4 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0252] Example 28

[0253] Using I-13 from Example 5 as the implementation object, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0254] Example 29

[0255] Using I-16 from Example 6 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0256] Example 30

[0257] Using I-19 from Example 7 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0258] Example 31

[0259] Using I-22 from Example 8 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0260] Example 32

[0261] Using I-25 from Example 9 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0262] Example 33

[0263] Using I-28 from Example 10 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0264] Example 34

[0265] Using I-31 from Example 11 as the implementation object, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0266] Example 35

[0267] Using I-34 from Example 12 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0268] Example 36

[0269] Using I-37 from Example 13 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0270] Example 37

[0271] Using I-40 from Example 14 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0272] Example 38

[0273] Using I-43 from Example 15 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0274] Example 39

[0275] Using I-46 from Example 16 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0276] Example 40

[0277] Using I-49 from Example 17 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0278] Example 41

[0279] Using I-52 from Example 18 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0280] Example 42

[0281] Using I-55 from Example 19 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0282] Example 43

[0283] Using I-58 from Example 20 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0284] Example 44

[0285] Using I-61 from Example 21 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0286] Example 45

[0287] Using I-64 from Example 22 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0288] Example 46

[0289] Using I-67 from Example 23 as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS (mass ratio 1:9) as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure described above, and the resulting device was tested.

[0290] Comparative Example 1

[0291] Using the compound (ppy)2Ir(mdp) without a solubilizing structure as the subject, its solubility in chlorobenzene was tested. It was mixed with 8CzTPS at a mass ratio of 1:9 as an organic light-emitting layer. An organic electroluminescent device was prepared using the device structure (which is the same as the device structure in Example 24, except that the organic light-emitting layer is different). The obtained device was then tested.

[0292] In Comparative Example 1 above, the chemical structure of compound (ppy)2Ir(mdp) is as follows:

[0293]

[0294] The green iridium complexes from Examples 24-46 and the compound (ppy)2Ir(mdp) from Comparative Example 1 were dissolved in chlorobenzene for solubility testing (the results are shown in Table 1). The performance of the resulting organic electroluminescent devices was then tested, and the results are shown in Table 1.

[0295] Table 1 Performance test results of the organic electroluminescent devices obtained in Examples 24-46 and Comparative Example 1

[0296] Device Example compound <![CDATA[Solubility [mg mL -1 > Start-up voltage [V] Maximum external quantum efficiency [%] T(95)[h] Example 24 I-1 50.4 3.4 18.6 287 Example 25 I-4 30.2 3.5 19.2 342 Example 26 I-7 60.3 3.3 17.8 215 Example 27 I-10 78.6 3.6 20.4 398 Example 28 I-13 54.6 3.2 18.1 256 Example 29 I-16 33.5 3.5 21.0 374 Example 30 I-19 68.4 3.4 17.3 301 Example 31 I-22 47.1 3.3 19.5 228 Example 32 I-25 76.8 3.6 20.7 389 Example 33 I-28 42.1 3.2 18.9 267 Example 34 I-31 59.3 3.5 17.6 413 Example 35 I-34 31.7 3.4 19.8 295 Example 36 I-37 65.9 3.3 20.2 336 Example 37 I-40 50.2 3.6 18.4 248 Example 38 I-43 73.5 3.2 21.0 372

[0297] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. The green iridium complex shown in Formula I: Formula I; in, n is an integer selected from 1 to 3; m1 to m7 are independently selected from integers between 0 and 4; q and p are independently selected from 0, 1, or 2; V1 and V2 are independently selected from one or more of the following: carbon-carbon single bond, -C-, -N-, -O-, -S-. R 1 ~R 7 It is independently selected from one or more of the following: H, D, -CN, -NO2, -CF3, -OH, -SH, -NH2, halogen, substituted or unsubstituted C1-C30 straight-chain or branched hydrocarbon group, C3-C30 cycloalkyl group, C1-C30 alkoxy group, C1-C30 alkylthio group, C6-C60 aryl group, C6-C60 aryl ether group, C5-C60 heteroaryl group, and C5-C60 heteroaryl ether group; , It is independently selected from one or more of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups; B1 and B2 are independently selected from H, aryl groups of C6 to C72, aryl amino groups of C6 to C30, substituted or unsubstituted straight-chain or branched alkyl groups of C1 to C10, and substituted or unsubstituted nitrogen-containing heteroaryl groups of C12 to C30.

2. The green iridium complex according to claim 1, characterized in that, The heteroatoms in the C5-C60 heteroaromatic or C5-C60 heteroaryl ether groups are independently selected from one or more of Si, Ge, N, P, O, S, and Se; The substituents of the C1-C30 straight-chain or branched hydrocarbon groups are selected from one or more of D, halogen, nitro, amino, and hydroxyl groups; The substituents of the C6-C30 aryl group or the C3-C30 heteroaryl group are independently selected from one or more of the following: C1-C10 straight-chain or branched alkyl groups, C1-C6 alkoxy groups, halogen groups, amino groups, and nitro groups. The substituents of the C1-C10 straight-chain or branched alkyl groups are selected from one or more of the aryl, halogen, amino, and nitro groups of C6-C12. The substituents of the nitrogen-containing heteroaryl group of C12 to C30 are selected from one or more of the following: heteroaryl group of C4 to C15, straight-chain or branched alkyl group of C1 to C10, alkoxy group of C1 to C6, halogen, amino group, and nitro group.

3. The green iridium complex according to claim 2, characterized in that, The , Independently selected from any of the structures shown in formulas A-1 to A-12: 。 4. The green iridium complex according to claim 3, characterized in that, B1 and B2 are independently selected from one or more of H, phenyl, biphenyl, terphenyl, polyphenyl, substituted or unsubstituted N-arylcarbazolyl, substituted or unsubstituted triphenylamine, and diphenylmethyl. The number of phenyl groups in the polyphenyl group is selected from an integer between 4 and 12; The substituents of the triphenylamine are selected from one or more of diphenylamino, halogen, nitro, and amino groups; The aryl group in the N-arylcarbazolyl group is selected from substituted or unsubstituted phenyl groups; The substituent of the phenyl group is selected from carbazolyl or carbazolyl-substituted carbazolyl; the substituent of the N-arylcarbazolyl group is selected from carbazolyl, and the number of carbazolyl groups is 1 or 2.

5. The green iridium complex according to claim 4, characterized in that, B1 and B2 are independently selected from any of the structures shown in formulas B-1 to B-27: 。 6. The green iridium complex according to any one of claims 1 to 5, characterized in that, The green iridium complex is selected from formula I. a ~I e Any of the structures shown: Equation I a ; Equation I b ; Equation I c ; Equation I d ; Formula I e .

7. The green iridium complex according to claim 6, characterized in that, The green iridium complex is selected from any of the structures shown in Formula I-1 to Formula I-69: 。 8. A luminescent material, characterized in that, Including the green iridium complex as described in any one of claims 1 to 7.

9. The luminescent material according to claim 8, characterized in that, The luminescent material also includes 8CzTPS; The mass ratio of the 8CzTPS to the green iridium complex is 1:(8~10).

10. An electroluminescent device, characterized in that, Includes the luminescent material as described in claim 8 or 9.

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