Spiro-containing platinum compound and organic light-emitting device

Abstract

The present invention relates to a spiro-containing platinum compound and an organic light-emitting device compound. The structure of the spiro-containing platinum compound is as shown in formula (I). Provided is a platinum compound of a spiro-containing ONCN tetradentate ligand. The material can improve the heavy-atom effect of a phosphorescent material, thereby improving the energy utilization rate of singlet and triplet excitons in the light emitting process. The spiro rings in the platinum compound provide sufficient 3D spatial configuration, thereby reducing the aggregation effect, further improving the luminous efficiency of the material, and providing the possibility for further industrialization of the material. The platinum compound is applied to an organic light-emitting diode and results in high efficiency and good thermal stability, photophysical properties, and device life.

Description

Spirocyclic platinum compounds and organic light-emitting devices Technical Field

[0001] The present application relates to the field of OLED phosphorescent materials, and in particular to spirocyclic platinum compounds and organic light-emitting devices. Background Art

[0002] OLEDs offer advantages such as thinness, light weight, self-luminescence, wide viewing angle, fast response, low energy consumption, excellent low-temperature and shock resistance, and the potential for flexible design. As all-solid-state devices, they lack a vacuum chamber and liquid components, making them vibration-resistant and easy to use. Their high resolution, wide viewing angle, and wide operating temperature range make them suitable for use as flat backlights and illumination sources in displays. Since the discovery of electrophosphorescence in 1998 by Professor Zhi Zhiming's team at the University of Hong Kong and Forrest et al. in the United States, organic electroluminescence technology has made significant progress. Researchers both domestically and internationally have been dedicated to bringing phosphorescent materials to industrial commercialization, focusing primarily on improving the performance of iridium compounds. Research has shown that organometallic compounds, due to their strong spin-orbit coupling (SOC), can achieve rapid intersystem crossing (ISC) and long-lived phosphorescent decay. Furthermore, phosphorescent materials can fully utilize the energy of singlet and triplet excitons during luminescence, improving the compound's luminescence efficiency and theoretically achieving 100% internal quantum efficiency in OLEDs. Consequently, over the past decade, organic transition metal compounds have become extremely attractive for use in electroluminescent devices such as organic light-emitting diodes (OLEDs). This new technology is enabling the development of highly efficient light-emitting systems. In the future, it will be possible to manufacture large, bright flat-panel displays at affordable prices. A key requirement for these applications is low power consumption and high efficiency in the light-emitting devices.

[0003] Summary of the Invention

[0004] To address the aforementioned issues with the existing technology, the present invention provides a platinum compound containing a spirocyclic ONCN tetradentate ligand. This material can enhance the heavy atom effect of phosphorescent materials, thereby improving the energy utilization of singlet and triplet excitons during luminescence. The spirocyclic ring in the platinum compound provides sufficient 3D spatial configuration, reducing aggregation effects and further improving the material's luminescence efficiency, thus opening up the possibility of further industrialization of this type of material.

[0005] The platinum compound is applied in organic light-emitting diodes and exhibits high efficiency, good thermal stability, photophysical properties and device life.

[0006] The structural formula of this type of spirocyclic platinum compound is shown in formula (I):

[0007] R1-R26 are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms, substituted or unsubstituted alkoxy having 1-20 carbon atoms, substituted or unsubstituted aryloxy having 6-30 carbon atoms, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted aryl having 6-40 carbon atoms, substituted or unsubstituted heteroalkyl having 3-40 carbon atoms, an aryl group, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted acyl group having 0 to 20 carbon atoms, a carbonyl group, a carboxylic acid group, a substituted or unsubstituted ester group having 0 to 20 carbon atoms, a cyano group, an isocyano group, a substituted or unsubstituted sulfanyl group having 0 to 20 carbon atoms, a substituted or unsubstituted sulfinyl group having 0 to 20 carbon atoms, a substituted or unsubstituted sulfonyl group having 0 to 20 carbon atoms, or a substituted or unsubstituted phosphine group having 0 to 20 carbon atoms;

[0008] Among them, R6-R 10 The adjacent groups in the sequence can be bonded to form a ring, R 15 -R 18 The adjacent groups in the sequence can be bonded to form a ring, R 19 -R 22 Adjacent groups in the sequence can bond to form a ring;

[0009] The substitution is substituted by deuterium, halogen, amino, nitro, cyano, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 10 carbon atoms or C1-C4 alkyl,

[0010] The heteroaryl and heteroalkyl groups contain at least one heteroatom selected from S, N, and O.

[0011] Among R23-R26, at least one of them is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, and substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms.

[0012] In some embodiments: R1-R22 are independently selected from hydrogen, deuterium, halogen, amine, carbonyl, carboxyl, substituted or unsubstituted sulfanyl having 1-20 carbon atoms, cyano, substituted or unsubstituted sulfonyl having 0-20 carbon atoms, substituted or unsubstituted phosphino having 0-20 carbon atoms, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted aryl having 6-10 carbon atoms, substituted or unsubstituted heteroaryl having 3-10 carbon atoms, substituted or unsubstituted alkylsilyl having 3-10 carbon atoms, substituted or unsubstituted arylsilyl having 6-10 carbon atoms;

[0013] wherein one of R23-R26 is selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms; and the remaining three are hydrogen.

[0014] The structural formula of this type of spiro-ring-containing platinum compound, in some embodiments, is shown in Formula (II):

[0015] Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group of 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group of 3 to 40 carbon atoms; n and m are integers of 0 to 2, and m+n≥1;

[0016] The R1-R 22 Consistent with the definition in claim 1;

[0017] The substitution is by deuterium, halogen, amino, nitro, cyano, aryl of 6-20 carbon atoms, heteroaryl of 5-10 carbon atoms

[0018] aryl or C1-C4 alkyl.

[0019] Ar1 is independently selected from a substituted or unsubstituted conjugated fused ring aromatic group of 6-20 carbon atoms, a substituted or unsubstituted conjugated fused ring heteroaromatic group of 6-20 carbon atoms, or a substituted or unsubstituted non-fused ring aromatic group of 6-20 carbon atoms; Ar2 is independently selected from a substituted or unsubstituted aromatic group of 6-20 carbon atoms, or a substituted or unsubstituted heteroaromatic group of 3-20 carbon atoms.

[0020] In some embodiments: R1-R22 is selected from hydrogen, deuterium, halogen, amine, cyano, substituted or unsubstituted alkyl having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl having 3-10 ring carbon atoms, substituted or unsubstituted aryl having 6-10 carbon atoms, substituted or unsubstituted heteroaryl having 3-10 carbon atoms, substituted or unsubstituted alkylsilyl having 3-10 carbon atoms, substituted or unsubstituted arylsilyl having 6-10 carbon atoms.

[0021] In some embodiments: among R1-R22, R7, R9, R13, R15-R22 are independently selected from hydrogen, deuterium, halogen, amine, cyano, alkyl of 1-6 carbon atoms, and the rest are hydrogen.

[0022] In some embodiments: Ar1 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracene, substituted or unsubstituted carbazolyl; Ar2 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorene, substituted or unsubstituted indolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted acridinyl, substituted or unsubstituted nitrogen or xanthenyl, substituted or unsubstituted phenanthrenyl, and n and m are integers from 0 to 1.

[0023] In some embodiments: wherein R1-R 22 In the middle, R7, R9, R 13 、R 16 、R 21 independently selected from hydrogen, deuterium or an alkyl group of 1 to 6 carbon atoms, the remainder being hydrogen;

[0024] Ar1 is selected from substituted or unsubstituted phenyl or carbazolyl, Ar2 is selected from substituted or unsubstituted phenyl or carbazolyl;

[0025] The substitution is substitution with deuterium, halogen, amino, nitro, cyano, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 10 carbon atoms or C1-C4 alkyl.

[0026] Examples of platinum compounds according to the present invention are listed below, but are not limited to the listed structures:

[0027] The precursor of the above compound has the structure shown in the following formula (III):

[0028] In some embodiments: the structure is shown in the following formula (IV):

[0029] An organic light-emitting device comprises a light-emitting layer, wherein the light-emitting layer comprises the above-mentioned platinum compound.

[0030] The platinum compound of the present invention is used as a phosphorescent doping material of a light-emitting layer in OLED.

[0031] The present invention improves material stability, device efficiency and service life through structural design.

[0032] This type of compound can improve the molecular spatial configuration, color purity and luminous efficiency by introducing spirofluorene.

[0033] This type of structure has more modifiable sites. In some embodiments, the increased steric hindrance of the Ar1 and Ar2 groups contained in the structure can effectively reduce intermolecular aggregation.

[0034] The platinum compound of the present invention has high fluorescence quantum efficiency, good thermal stability and low quenching constant, and can be used to manufacture green light OLED devices with high luminous efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] FIG1 is a structural diagram of the device of the present invention. DETAILED DESCRIPTION

[0036] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0037] Example 1: Synthesis of Intermediate Structure M

[0038] Synthesis of intermediate C

[0039] In a 500ml three-necked flask, A (10.0g, 53.5mmol, 1.1eq.) was dissolved in diethyl ether (100ml). The mixture was cooled to -78°C under nitrogen. A 1.6M n-butyllithium solution in n-hexane (33.4ml) was added dropwise to the solution, and the mixture was stirred for 30 minutes. Subsequently, the reaction solution was added dropwise to a solution of B (12.4g) in diethyl ether (100ml) at -78°C. The mixture was stirred at room temperature overnight, and water was added to the mixture. Extraction was performed three times with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluting solvent: n-hexane / ethyl acetate = 10:1 (v / v)) to obtain 11.2g (80% yield) of a yellow oil.

[0040] Synthesis of intermediate E

[0041] In a 500ml three-necked flask, C (11.2g, 38.6mmol, 1.0eq.) was dissolved in anhydrous THF (100ml). The mixture was cooled to -78°C under nitrogen, and D (38.6mmol) was added dropwise to the solution. The mixture was stirred at room temperature for 24 hours. The reaction solution was quenched with a saturated ammonium chloride solution and extracted three times with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluting solvent: hexane / ethyl acetate = 1:5 (v / v)) to obtain a yellow oil, which was dissolved in acetic acid (100ml) and placed in a 500ml three-necked flask. Concentrated sulfuric acid (2ml) and acetic anhydride (2ml) were then added. The reaction was stirred at 130°C under nitrogen for 12 hours. TLC monitoring was performed until the reaction was complete. After the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the pH was adjusted to a weak base with saturated sodium carbonate solution. Ethyl acetate was then added for extraction three times, the combined organic phases were dried over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure. The crude product was separated by silica gel chromatography using n-hexane / ethyl acetate = 20:1-10:1 (V / V) as eluent to obtain 13.7 g of a yellow solid with a yield of 83.5%.

[0042] Synthesis of intermediate F

[0043] To a 500 mL three-necked flask, add anhydrous THF (150 mL) and Mg (770.4 mg, 32.1 mmol, 1.0 eq). Heat to 50°C under nitrogen. Add a THF solution of E (13.7 g, 32.1 mmol, 1.0 eq) (50 mL) over 30 minutes and stir until all the Mg has dissolved. The temperature is then lowered to -10°C, and a THF solution of acetic anhydride (6.6 g, 64.2 mmol, 2.0 eq) (50 mL) is added dropwise over one hour. The reaction is continued at room temperature until complete as determined by TLC. The reaction solution is quenched with saturated ammonium chloride solution and extracted three times with ethyl acetate. The organic layer is washed with saturated brine, dried over anhydrous sodium sulfate, and the filtrate is concentrated under reduced pressure. The residue is purified by silica gel column chromatography (eluting solvent: n-hexane / ethyl acetate = 10:1, (v / v)) to yield 10.2 g of a white solid in 82% yield.

[0044] Synthesis of intermediate G

[0045] In a 500ml single-necked flask, add F (10.2g, 26.0mmol, 1.0eq), pyridine hydrochloride (102g, mass ratio 10), and o-dichlorobenzene (10ml). Under nitrogen, react in an oil bath at 200°C for 8 hours, then cool to room temperature. Dissolve the mixture in a large amount of water and extract three times with DCM. The organic phase is then dried and chromatographed on a silica gel column (chromatographic solvent: n-hexane / ethyl acetate = 5:1, (v / v)) to give 9.3g of a pale yellow solid (95% yield).

[0046] Synthesis of intermediate H

[0047] In a 500ml three-necked flask, add G (9.3g, 24.7mmol, 1.0eq), pyridine (3.9g, 49.4mmol, 2.0eq), and DCM (100ml). Under nitrogen, add Tf2O (8.4g, 29.6mmol, 1.2eq) dropwise over 30min in an ice bath and stir at room temperature overnight. Wash three times with saturated brine. The organic phase is then dried and chromatographed on a silica gel column (chromatographic solvent: n-hexane / ethyl acetate = 10:1, (v / v)) to give 11.7g of a yellow solid in a 93% yield.

[0048] Synthesis of intermediate I

[0049] In a 500ml single-flask, add H (11.7g, 22.9mmol, 1.0eq), I2 (6.9g, 27.48mmol, 1.2eq), and pyridine (100ml). Stir at 130°C under nitrogen for 16h. After the reaction, filter directly and slurry the solid twice with methanol. 14.6g of off-white solid is obtained, with a yield of 89%.

[0050] Synthesis of intermediate L

[0051] Take a 500ml single-necked bottle, put J (5g, 33.3mmol, 1.0eq), K (8.7g, 40mmol, 1.05eq) and KOH (9.3g, 166.5mmol, 5.0eq) into CH3OH (100ml), replace nitrogen, and react at 45°C for 16h; after the reaction, filter to obtain a yellow solid, then heat slurry with n-hexane (50mL) at 60°C for 2h, filter to obtain 8.7g of a white solid, with a yield of 80%.

[0052] Synthesis of intermediate M

[0053] In a 500ml single-necked flask, L (6.5g, 18.5mmol, 1.0eq), I (14.6g, 20.4mmol, 1.1eq), NH4OAc (65g, mass ratio 10), and AcOH (130ml) were added under nitrogen and reacted at 130°C for 16h. After completion of the reaction, the combined products were added with water (300mL) and filtered to obtain a yellow solid. Rapid separation on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1, (v / v)) afforded 14.2g of a white solid with a yield of 81%.

[0054] Example 1: Synthesis of Compound 114

[0055] Synthesis of intermediate 114b

[0056] In a 250 ml single-necked flask, M (5 g, 5.96 mmol, 1.0 eq), 25a (872 mg, 7.15 mmol, 1.2 eq), Pd(PPh3)4 (344 mg, 0.298 mmol, 0.05 eq), and K3PO4 (2.53 g, 11.92 mmol, 2 eq) were dissolved in Tol / EtOH / H2O (30 ml / 30 ml / 15 ml). The atmosphere was replaced with nitrogen and the reaction was carried out at 80°C for 16 h. After completion of the reaction, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was purified by rapid chromatography on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1, (v / v)) to give 3.88 g of a white solid in 85% yield.

[0057] Synthesis of intermediate 114c

[0058] In a 100ml single-necked flask, 25b (3.88g), pyridine hydrochloride (38.8g), and o-dichlorobenzene (4.0ml) were added. Under nitrogen, the mixture was reacted in an oil bath at 200°C for 8 hours, then cooled to room temperature. The mixture was dissolved in a large amount of water and extracted three times with DCM. The organic phase was dried and subjected to silica gel column chromatography (chromatographic solvent: hex:EA = 10:1, (v / v)) to give 3.5g of a pale yellow product in a 92% yield.

[0059] Synthesis of compound 114

[0060] In a 250ml single-necked flask, 2c (100mg, 0.116mmol), K2PtCl4 (57mg, 0.139mmol), TBAB (4mg, 0.012mmol), and acetic acid (5mL) were added under nitrogen atmosphere at 130°C for 48h. After completion of the reaction, an excess of deionized water was added to allow the precipitated solid to separate. The solid was then filtered and dissolved in dichloromethane, dried, and passed through a silica gel column (Hex:DCM:EA = 20:20:1 (v / v / v)). The product was recrystallized from dichloromethane:n-hexane = 1:4 (v / v) to yield 80mg of a red solid.

[0061] 1 H NMR(500MHz,Chloroform-d)δ8.58(d,J=5.0Hz,1H),7.99(dd,J=7.5,2.0Hz,1H),7.88(s,2H),7.74-7.69(m,3H),7.67-7.63(m,2H), 7.62-7.58(m,2H),7.49-7.35(m,13H),7.32(d,J=2.0Hz,2H),7.23(td,J=7.5,2.0Hz,1H),7.19(dd,J=7.4,2.0Hz,1H),1.36(s,18H).

[0062] Example 2: Synthesis of Compound 9

[0063] Synthesis of intermediate 9b

[0064] In a 250 ml single-necked flask, M (5 g, 5.96 mmol, 1.0 eq), 9a (1.79 g, 7.15 mmol, 1.2 eq), Pd(PPh3)4 (304 mg, 0.26 mmol, 0.05 eq), and K3PO4 (2.23 g, 10.52 mmol, 2 eq) were dissolved in Tol / EtOH / H2O (30 ml / 30 ml / 15 ml). The atmosphere was replaced with nitrogen and the reaction was carried out at 80°C for 16 h. After completion of the reaction, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was purified by rapid chromatography on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1 (v / v)) to give 4.78 g of a white solid in 87% yield.

[0065] Synthesis of intermediate 9c

[0066] In a 100ml single-necked flask, 9b (4.78g), pyridine hydrochloride (37.8g), and o-dichlorobenzene (5ml) were added. Under nitrogen protection, the oil bath temperature was 200°C and the reaction was allowed to react for 8 hours, then cooled to room temperature. The mixture was dissolved in a large amount of water and extracted three times with DCM. The organic phase was spin-dried and subjected to silica gel column chromatography (chromatographic solvent: n-hexane:ethyl acetate = 10:1 (v / v)) to obtain 4.37g of a light yellow product with a yield of 93%. Synthesis of Compound 9

[0067] In a 250ml single-necked flask, add 9c (100mg, 0.11mmol), K2PtCl4 (57mg, 0.139mmol), TBAB (4mg, 0.011mmol), and acetic acid (5mL) under nitrogen atmosphere at 130°C for 48h. After completion of the reaction, add excess deionized water to precipitate a solid, which is then filtered and dissolved in dichloromethane. The solid is then spin-dried and passed through a silica gel column (Hex:DCM:EA = 20:20:1, v / v / v). The product is recrystallized from dichloromethane:n-hexane = 1:4 (v / v) to yield 90mg of a red solid.

[0068] 1 H NMR(500MHz,Chloroform-d)δ8.47(d,J=4.9Hz,1H),8.20(s,1H),8.13(s,1H),7. 99(dd,J=7.5,2.0Hz,1H),7.88(s,2H),7.79(s,1H),7.75-7.70(m,2H),7.70-7.6 2(m,4H),7.57(s,1H),7.50-7.37(m,16H),7.35(s,1H),7.32(d,J=2.0Hz,2H),7. 26(s,1H),7.23(td,J=7.5,2.0Hz,1H),7.19(dd,J=7.4,2.0Hz,1H),1.36(s,18H).

[0069] Example 3: Synthesis of Compound 5

[0070] Synthesis of intermediate 5c

[0071] In a 250 ml single-necked flask, 5a (5 g, 17.4 mmol, 1.0 eq), 5b (4.14 g, 17.4 mmol, 1.0 eq), Pd(dppf)Cl2 (635 mg, 0.87 mmol, 0.05 eq), and Cs2CO3 (11.3 g, 34.8 mmol, 2 eq) were dissolved in dioxane (50 ml). The atmosphere was replaced with nitrogen and the reaction was carried out at 100°C for 16 h. After completion of the reaction, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was purified by rapid chromatography on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1, (v / v)) to give 4.88 g of a white solid in 80% yield.

[0072] Synthesis of intermediate 5d

[0073] In a 250 ml single-necked flask, 5c (4.88 g, 13.8 mmol, 1.0 eq), Bpin2 (5.25 g, 20.7 mmol, 1.5 eq), Pd(dppf)Cl2 (504 mg, 0.69 mmol, 0.05 eq), and KOAc (2.7 g, 27.6 mmol, 2 eq) were dissolved in toluene (50 ml). The atmosphere was replaced with nitrogen and the reaction was allowed to proceed at 100°C for 16 h. After completion of the reaction, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was purified by rapid chromatography on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1 (v / v)) to afford 5.2 g of a white solid in 85% yield.

[0074] Synthesis of intermediate 5e

[0075] In a 250 ml single-necked flask, M (5 g, 5.96 mmol, 1.0 eq), 5d (2.77 g, 7.15 mmol, 1.2 eq), Pd(PPh3)4 (304 mg, 0.26 mmol, 0.05 eq), and K3PO4 (2.23 g, 10.52 mmol, 2 eq) were dissolved in Tol / EtOH / H2O (30 ml / 30 ml / 15 ml). The atmosphere was replaced with nitrogen and the reaction was carried out at 80°C for 16 h. After completion of the reaction, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was purified by rapid chromatography on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1, (v / v)) to give 4.8 g of a white solid in 80% yield.

[0076] Synthesis of intermediate 5f

[0077] In a 100ml single-necked flask, add 5e (4.8g), pyridine hydrochloride (48g), and o-dichlorobenzene (5ml). Under nitrogen, react in an oil bath at 200°C for 8 hours, then cool to room temperature. Dissolve with copious amounts of water and extract three times with DCM. The organic phase is then dried and chromatographed on a silica gel column (chromatographic solvent: n-hexane:ethyl acetate = 10:1, (v / v)) to give 4.32g of a pale yellow product in a 92% yield.

[0078] Synthesis of compound 5

[0079] In a 250ml single-necked flask, add 5f (100mg, 0.1mmol), K2PtCl4 (45mg, 0.12mmol), TBAB (3mg, 0.01mmol), and acetic acid (5mL) under nitrogen atmosphere at 130°C for 48h. After completion of the reaction, add excess deionized water to precipitate a solid, which is then filtered and dissolved in dichloromethane. The solid is then spin-dried and passed through a silica gel column (Hex:DCM:EA = 20:20:1, (v / v / v)). The product is recrystallized from dichloromethane:n-hexane = 1:4 (v / v) to yield 85mg of a red solid.

[0080] 1 H NMR(500MHz,Chloroform-d)δ8.47(d,J=4.9Hz,1H),8.20(s,1H),8.13(s,1H),7.99(dd ,J=7.5,2.0Hz,1H),7.88(s,2H),7.85(s,1H),7.75-7.70(m,2H),7.69-7.67(m,2H),7.6 6-7.62(m,3H),7.62-7.58(m,2H),7.56-7.36(m,17H),7.35(s,1H),7.32(d,J=2.0Hz,2 H),7.26(s,1H),7.23(td,J=7.5,2.0Hz,1H),7.19(dd,J=7.4,2.0Hz,1H),1.36(s,18H).

[0081] Example 4: Synthesis of Compound 12

[0082] Synthesis of intermediate 12c

[0083] In a 1000ml single-necked flask, 12a (20g, 74.29mmol, 1.0eq), 12b (12.66g, 81.72mmol, 1.1eq), Pd(dppf)Cl2 (2.72g, 3.71mmol, 0.05eq), K2CO3 (30.8g, 222.87mmol, 3.0eq), and toluene / ethanol / water (400ml / 100ml / 100ml) were added. The mixture was stirred at 60°C for 6h under nitrogen atmosphere. After completion of the reaction, most of the solvent was evaporated, water was added, and the product was extracted three times with DCM (50ml). The product was then evaporated and separated by silica gel column chromatography (eluent: n-hexane:ethyl acetate = 5:1 (v / v)). 20g of a yellow oil was obtained with a yield of 95.6%.

[0084] Synthesis of intermediate 12d

[0085] Take a 1000ml single-necked bottle and put 12c (20g, 71.06mmol, 1.0eq), CuI (17.59g, 92.38mmol, 1.3eq), t BuONO (36.64 g, 36.64 g, 5.0 eq) and acetonitrile (400 ml) were reacted at 55°C for 4 h under nitrogen. After completion of the reaction, the mixture was quickly filtered through a silica gel funnel (eluent: ethyl acetate), spin-dried, and separated by silica gel column chromatography (eluent: n-hexane) to obtain 20 g of a white solid with a yield of 71.7%.

[0086] Synthesis of intermediate 12f

[0087] In a 250 ml single-necked flask, 12e (5 g, 23.7 mmol, 1.0 eq), 38b (6.77 g, 28.4 mmol, 1.2 eq), Pd(dppf)Cl2 (866 mg, 1.18 mmol, 0.05 eq), and Cs2CO3 (15.4 g, 47.4 mmol, 2 eq) were dissolved in toluene (100 ml). The atmosphere was replaced with nitrogen and the reaction was carried out at 100°C for 16 h. After completion of the reaction, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was purified by rapid chromatography on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1, (v / v)) to give 5.28 g of a white solid in 80% yield.

[0088] Synthesis of intermediate 12g

[0089] In a 250 ml single-necked flask, 12f (5.28 g, 19.0 mmol, 1.0 eq), 12d (11.17 g, 28.5 mmol, 1.5 eq), Cu (608 mg, 9.5 mmol, 0.5 eq), CuI (1.8 mg, 9.5 mmol, 0.5 eq), o-phenanthroline (3.42 g, 19.0 mmol, 1.0 eq), Cs2CO3 (18.53 g, 57.0 mmol, 3.0 eq), and xylene (150 ml) were added under nitrogen at 140°C for 48 h. After completion of the reaction, the mixture was quickly filtered through a silica gel funnel (EA), the solvent was dried, and the product was separated by silica gel column chromatography (eluent: n-hexane:ethyl acetate = 10:1 (v / v)). 7.6 g of a white solid was obtained with a yield of 74%.

[0090] Synthesis of intermediate 12h

[0091] In a 250 ml single-necked flask, 12 g (7.6 g, 14.0 mmol, 1.0 eq), Bpin2 (5.33 g, 21.0 mmol, 1.5 eq), Pd(dppf)Cl2 (511 mg, 0.7 mmol, 0.05 eq), and K2CO3 (3.86 g, 28.0 mmol, 2 eq) were dissolved in toluene (100 ml), the atmosphere was replaced with nitrogen, and the reaction was carried out at 100°C for 16 h. After the reaction was completed, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was rapidly separated on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1, (v / v)) to obtain 7.1 g of a white solid with a yield of 80%.

[0092] Synthesis of intermediate 12i

[0093] In a 250 ml single-necked flask, M (5 g, 5.96 mmol, 1.0 eq), 12h (3.95 g, 7.15 mmol, 1.2 eq), Pd(PPh3)4 (304 mg, 0.26 mmol, 0.05 eq), and K3PO4 (2.23 g, 10.52 mmol, 2 eq) were dissolved in Tol / EtOH / H2O (30 ml / 30 ml / 15 ml). The atmosphere was replaced with N2 and the reaction was carried out at 80°C for 16 h. After completion of the reaction, the reaction was filtered, the filtrate was concentrated in vacuo, and the residue was subjected to rapid separation on a silica gel column (eluent: n-hexane / ethyl acetate = 10:1, (v / v)) to give 5.68 g of a white solid with a yield of 80%.

[0094] Synthesis of intermediate 12j

[0095] In a 100ml single-necked bottle, 12i (5.68g), pyridine hydrochloride (56.8g), and o-dichlorobenzene (6ml) were added. Under nitrogen protection, the oil bath temperature was 200°C and the reaction was allowed to react for 8 hours, then cooled to room temperature. The mixture was dissolved in a large amount of water and extracted three times with DCM. The organic phase was spin-dried and subjected to silica gel column chromatography (chromatographic solvent: n-hexane:ethyl acetate = 5:1, (v / v)) to obtain 5.2g of a light yellow product with a yield of 93%. Synthesis of Compound 12

[0096] In a 250ml single-necked flask, 12j (200mg, 0.17mmol), K2PtCl4 (76mg, 0.20mmol), TBAB (5mg, 0.017mmol), and acetic acid (5mL) were added under nitrogen atmosphere at 130°C for 48h. After completion of the reaction, an excess of deionized water was added to allow the precipitated solid to precipitate. The solid was then filtered and dissolved in dichloromethane, dried, and passed through a silica gel column (Hex:DCM:EA = 20:20:1, (v / v / v)). The product was recrystallized from dichloromethane:n-hexane = 1:4 (v / v) to yield 150mg of a red solid.

[0097] 1 H NMR(500MHz,Chloroform-d)δ8.47(d,J=4.9Hz,1H),8.20(s,1H),8.13(s,1H),7.99(dd,J=7.5,2 .0Hz,1H),7.88(s,2H),7.85(s,1H),7.82(t,J=1.9Hz,1H),7.75-7.70(m,2H),7.69-7.66(m,2H), 7.66-7.62(m,3H),7.62-7.59(m,2H),7.56-7.49(m,2H),7.49-7.37(m,15H),7.35(s,1H),7.33- 7.28(m,2H),7.26(s,1H),7.23(td,J=7.5,2.0Hz,1H),7.19(dd,J=7.4,2.0Hz,1H),1.36(s,36H).

[0098] Example 5:

[0099] An organic light emitting diode is prepared using the compound luminescent material of the present invention, and the device structure is shown in FIG1 .

[0100] First, a transparent conductive ITO glass substrate (with an anode ITO (20 in the figure)) is washed sequentially with a detergent solution and deionized water, ethanol, acetone, and deionized water, and then treated with oxygen plasma for 30 seconds.

[0101] Then, HATCN was evaporated on the ITO to a thickness of 10 nm as a hole injection layer (30 in the figure).

[0102] Then, compound HT was evaporated to form a 40 nm thick hole transport layer (40 in the figure).

[0103] Then, a 20 nm thick light-emitting layer (50 in the figure) is evaporated on the hole transport layer. The light-emitting layer is composed of a mixed doping of platinum compound 114 (20%) and CBP (80%).

[0104] Then, AlQ3 was evaporated on the light-emitting layer to a thickness of 40 nm as an electron transport layer (60 in the figure).

[0105] Finally, 1 nm LiF was evaporated to form the electron injection layer 70 and 100 nm Al was deposited to form the device cathode (80 in the figure).

[0106] Example 6: Compound 9 was used instead of Compound 114, and an organic light emitting diode was prepared using the method described in Example 5.

[0107] Example 7: Compound 5 was used instead of Compound 114, and an organic light emitting diode was prepared using the method described in Example 5.

[0108] Example 8: Using compound 12 instead of compound 114, an organic light emitting diode was prepared using the method described in Example 5.

[0109] Comparative Example 1:

[0110] An organic light-emitting diode was prepared by the method described in Example 5, using compound Ref-1 (CN110872325A) instead of compound 114.

[0111] Comparative Example 2:

[0112] An organic light-emitting diode was prepared by the method described in Example 5, using compound Ref-3 (CN110872325A) instead of compound 114.

[0113] Comparative Example 3:

[0114] An organic light-emitting diode was prepared by the method described in Example 5 using compound Ref-4 (CN110872325A) instead of compound 114.

[0115] The structural formulas of HATCN, HT, AlQ3, Ref-1, Ref-2, Ref-3 and CBP in the device are as follows:

[0116] The organic electroluminescent devices in Examples 5-8 and Comparative Examples 1-3 were 2 The device performance at the current density is listed in the table below:

[0117] The data in the table demonstrates that, under the same conditions, the platinum compound materials of the present invention exhibit lower driving voltages and higher luminous efficiency when applied to organic light-emitting diodes. Furthermore, the device lifespan of organic light-emitting diodes based on the compounds of the present invention significantly outperforms the compound materials in the comparative examples, meeting the display industry's requirements for luminescent materials and demonstrating promising industrial prospects.

[0118] The above-described various embodiments are intended to be illustrative only and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, the various materials and structures described herein may be replaced with other materials and structures. It should be understood that those skilled in the art can make numerous modifications and variations based on the principles of the present invention without requiring creative effort. Therefore, any technical solutions that can be derived from existing technologies through analysis, reasoning, or partial research should fall within the scope of protection defined by the claims.

Claims

1. A platinum compound containing a spiro ring, the structural formula of which is shown in formula (I): R1-R 26 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 40 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted acyl group having 0 to 20 carbon atoms, a carbonyl group, a carboxylic acid group, a substituted or unsubstituted ester group having 0 to 20 carbon atoms, a cyano group, an isocyano group, a substituted or unsubstituted sulfanyl group having 0 to 20 carbon atoms, a substituted or unsubstituted sulfinyl group having 0 to 20 carbon atoms, a substituted or unsubstituted sulfonyl group having 0 to 20 carbon atoms, or a substituted or unsubstituted phosphinoyl group having 0 to 20 carbon atoms; in, R6-R 10 The adjacent groups in the sequence can be bonded to form a ring, R 15 -R 18 The adjacent groups in the sequence can be bonded to form a ring, R 19 -R 22 Adjacent groups in the sequence can bond to form a ring; The substitution is substituted by deuterium, halogen, amino, nitro, cyano, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 10 carbon atoms or C1-C4 alkyl, The heteroaryl and heteroalkyl groups contain at least one heteroatom selected from S, N, and O.

2. The spiro-ring-containing platinum compound according to claim 1, wherein R 23 -R 26 At least one of the following is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 40 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, and substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms.

3. The spiro-ring-containing platinum compound according to claim 2, wherein R1-R 22 are each independently selected from hydrogen, deuterium, halogen, amino, carbonyl, carboxyl, substituted or unsubstituted sulfanyl having 1 to 20 carbon atoms, cyano, substituted or unsubstituted sulfonyl having 0 to 20 carbon atoms, substituted or unsubstituted phosphinoyl having 0 to 20 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 10 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 10 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 10 carbon atoms; R 23 -R 26 wherein one of the groups is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms; and the remaining three are hydrogen.

4. The spiro ring-containing platinum compound according to claim 1, having a structural formula as shown in formula (II): Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group of 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group of 3 to 40 carbon atoms; n and m are integers of 0 to 2, and m+n≥1; The R1-R 22 Consistent with the definition in claim 1; The substitution is substitution with deuterium, halogen, amino, nitro, cyano, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 10 carbon atoms or C1-C4 alkyl.

5. The spiro ring-containing platinum compound according to claim 4, wherein Ar1 is independently selected from a substituted or unsubstituted conjugated fused ring aromatic group having 6 to 20 carbon atoms, a substituted or unsubstituted conjugated fused ring heteroaromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted non-fused ring aromatic group having 6 to 20 carbon atoms, and Ar2 is independently selected from a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 3 to 20 carbon atoms.

6. The spiro-ring-containing platinum compound according to claim 5, wherein R1-R 22 is selected from hydrogen, deuterium, halogen, amino, cyano, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 10 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 10 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 10 carbon atoms.

7. The spiro ring-containing platinum compound according to claim 6, wherein R1-R 22 In the middle, R7, R9, R 13 、R 15 -R 22 Independently selected from hydrogen, deuterium, halogen, amino, cyano, alkyl of 1 to 6 carbon atoms, and the rest are hydrogen.

8. The spiro ring-containing platinum compound according to claim 7, wherein Ar1 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, or substituted or unsubstituted carbazolyl; Ar2 is selected from phenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted indolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted acridinyl, substituted or unsubstituted nitrogen or xanthenyl, or substituted or unsubstituted phenanthryl, and n and m are integers from 0 to 1.

9. The spiro ring-containing platinum compound according to claim 8, wherein R1-R 22 In the middle, R7, R9, R 13 、R 16 、R 21 independently selected from hydrogen, deuterium or an alkyl group of 1 to 6 carbon atoms, the remainder being hydrogen; Ar1 is selected from substituted or unsubstituted phenyl or carbazolyl, Ar2 is selected from substituted or unsubstituted phenyl or carbazolyl; The substitution is substitution with deuterium, halogen, amino, nitro, cyano, aryl of 6 to 20 carbon atoms, heteroaryl of 5 to 10 carbon atoms or C1-C4 alkyl.

10. The spiro ring-containing platinum compound according to claim 1, having one of the following structures:

11. The precursor of the spiro ring-containing platinum compound according to any one of claims 1 to 3, having a structure as shown in the following formula (III): Where R1-R 26 The definition as described in any one of claims 1-3.

12. The precursor according to claim 11, having a structure as shown in the following formula (IV): wherein Ar1, Ar2, n, and m are as defined in any one of claims 4 to 8.

13. An organic light-emitting device comprising a light-emitting layer, wherein the light-emitting layer comprises the platinum compound according to any one of claims 1 to 10.

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