Carbazole-Modified Platinum Complex Luminescent Materials and Their Applications

Abstract

The present invention relates to a carbazole-modified platinum complex luminescent material and its applications. The platinum complex is a compound having the structure of chemical formula (I). The nitrogen-containing fused ring contained in this series of materials accelerates the triplet radiative transition rate by changing the spin density distribution. This series of materials inhibits molecular aggregation through carbazole modification, reducing the intermolecular π-π effect; while improving the molecular thermal stability, it also improves the luminescence efficiency of the molecule. When this compound is applied in an organic light-emitting diode, it has a low driving voltage and a high luminescence efficiency, and can significantly improve the luminescence efficiency of the material and the device lifetime, and has the potential to be applied in the field of organic electroluminescent devices.

Description

Technical Field

[0001] The present invention relates to the field of luminescent materials, and particularly to a platinum complex luminescent material containing a carbazole group-modified ONCN tetradentate ligand and its application in organic light-emitting diodes. Background Art

[0002] Organic Light-Emitting Diode (OLED) was discovered by the Chinese-American professor Ching W. Tang in the laboratory in 1979. Due to its advantages such as self-luminescence, wide viewing angle, almost infinitely high contrast ratio, low power consumption, extremely high response speed, and potential flexibility and foldability, it has always received extensive attention and research. In the field of OLED materials, phosphorescent OLED luminescent layer doping materials have developed relatively rapidly and maturely, which are mainly based on some heavy metal organic complexes. Phosphorescent materials can make full use of the energy of singlet and triplet excitons during the luminescence process. Therefore, theoretically, their quantum efficiency can reach 100%, and they are currently the most widely used luminescent materials in the industry. Metal complex luminescent materials have been applied in the industry. Traditional industrial phosphorescent OLED luminescent layer doping materials are mainly based on metal iridium complexes. Platinum metal has a natural advantage over iridium in price, and its complexes have also been greatly developed in recent years due to their excellent material stability caused by their planarity. In recent years, metal platinum complexes have shown properties that can catch up with iridium complexes, but in terms of performance, such as luminescence efficiency and service life, they still need to be further improved. Luminescent materials with higher efficiency and longer service life are urgently needed in the current industrial community. The platinum complex molecules of ONCN tetradentate ligands have simple synthesis steps, have more modifiable sites, and have great room for improvement. At the same time, carbazole, as one of the most commonly used high-efficiency conjugated modification groups since the beginning of OLED materials, can well solve the material efficiency problem. Summary of the Invention

[0003] In view of the above problems existing in the prior art, the present invention provides a class of platinum complex luminescent materials based on carbazole-modified ONCN tetradentate ligands. The nitrogen-containing fused rings contained in this series of materials change the spin density distribution and accelerate the triplet radiative transition speed. This series of materials inhibits molecular aggregation through carbazole modification, reduces the intermolecular π-π effect; while improving the molecular thermal stability, it also improves the luminescence efficiency of the molecules.

[0004] The present invention also provides an organic light-emitting diode containing the platinum complex luminescent material. The application of this platinum complex in an organic light-emitting diode exhibits good optoelectronic properties and device life.

[0005] The platinum complex based on the carbazole-modified ONCN tetradentate ligand is a compound having the structure of formula (I):

[0006]

[0007] Wherein:

[0008] X 1 to X 14 are each independently selected from N, C or CR 0 ;

[0009] R 0 -R 4 are each independently selected from the following groups: hydrogen, deuterium, halogen, amino, carbonyl, carboxyl, thioalkyl, cyano, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted alkoxy having 1-20 carbon atoms, substituted or unsubstituted aryl having 6-30 carbon atoms, or substituted or unsubstituted heteroaryl having 3-30 carbon atoms;

[0010] Adjacent R 0 -R 4 groups can optionally be connected to form a ring;

[0011] Said substitution is by halogen, amino, cyano or C 1 -C 4 alkyl;

[0012] The heteroatoms in said heteroaryl are one or more of N, S, O.

[0013] Preferably, R 0 -R 4 are each independently selected from: hydrogen, deuterium, halogen, amino, thioalkyl, cyano, substituted or unsubstituted alkyl having 1-6 carbon atoms, substituted or unsubstituted cycloalkyl having 3-6 ring carbon atoms, substituted or unsubstituted alkenyl having 2-6 carbon atoms, substituted or unsubstituted alkoxy having 1-6 carbon atoms, substituted or unsubstituted aryl having 6-12 carbon atoms, or substituted or unsubstituted heteroaryl having 3-6 carbon atoms.

[0014] Preferably, R 0 、R 2 -R 3 are each independently selected from: hydrogen, deuterium, halogen, C 1 -C 4 alkyl, cyano, substituted or unsubstituted cycloalkyl having 3-6 ring carbon atoms, substituted or unsubstituted aryl having 6-12 carbon atoms, substituted or unsubstituted heteroaryl having 3-6 carbon atoms;

[0015] R 1, R 4 Selected from substituted or unsubstituted cycloalkyl having 3 - 6 ring carbon atoms, substituted or unsubstituted aryl having 6 - 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 - 6 carbon atoms.

[0016] Preferably, R 0 , R 2 -R 3 Each independently selected from: hydrogen, deuterium, methyl, isopropyl, isobutyl, tert - butyl, cyano, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrimidinyl;

[0017] R 1 , R 4 Selected from substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted naphthyl, substituted or unsubstituted quinolinyl.

[0018] Preferably: wherein, X 1 to X 7 , X 9 -X 10 Each independently CR 0 ; X 8 is C, X 11 to X 14 Each independently CR 0 or N; and only one of X 11 to X 14 is N.

[0019] Wherein, R 0 Each independently selected from: hydrogen, deuterium, methyl, isopropyl, isobutyl, tert - butyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl; R 2 -R 3 Each independently selected from: hydrogen, deuterium, methyl, isopropyl, isobutyl, tert - butyl; R 1 , R 4 Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl.

[0020] Examples of the platinum complexes according to the present invention are listed below, but are not limited to the structures listed:

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029] The precursor of the above metal complex, i.e., the ligand, has the following structural formula:

[0030]

[0031] The present invention also provides an application of the above platinum complex in an organic optoelectronic device, and the optoelectronic device includes, but is not limited to, an organic light-emitting diode, an organic thin-film transistor, an organic photovoltaic device, a light-emitting electrochemical cell, and a chemical sensor, preferably an organic light-emitting diode.

[0032] The organic light-emitting diode in the present invention includes a cathode, an anode, and an organic layer. The organic layer is one or more layers of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer, and an electron transport layer, and it is not necessary for each of these organic layers to exist; at least one of the hole injection layer, the hole transport layer, the hole blocking layer, the electron injection layer, the light-emitting layer, and the electron transport layer contains the platinum complex represented by formula (I).

[0033] Preferably, the layer where the platinum complex represented by formula (I) is located is the light-emitting layer or the electron transport layer.

[0034] The total thickness of the organic layer of the device of the present invention is 1 - 1000 nm, preferably 1 - 500 nm, and more preferably 5 - 300 nm.

[0035] The organic layer can form a thin film by evaporation or solution method.

[0036] A series of platinum complex luminescent materials disclosed in the present invention have good luminescent properties and can be used as luminescent materials in organic light-emitting diodes.

[0037] When this compound is applied in an organic light-emitting diode, it has a lower driving voltage and a higher luminescent efficiency, and can significantly improve the service life of the device, and has the potential to be applied in the field of organic electroluminescent devices. Description of the Drawings

[0038] Figure 1Structural diagram of the organic light-emitting diode device of the present invention

[0039] Among them, 10 represents a glass substrate, 20 represents an anode, 30 represents a hole injection layer, 40 represents a hole transport layer, 50 represents a light-emitting layer, 60 represents an electron transport layer, 70 represents an electron injection layer, and 80 represents a cathode. Specific implementation mode

[0040] Example 1: Synthesis of compound C

[0041]

[0042] Take a 250 ml single-necked flask, add A (10.0 g, 53 mmol, 1.0 eq), B (12.5 g, 53 mmol, 1.0 eq), Na 2 S 2 O 5 (508 mg, 2.6 mmol, 0.05 eq), DMF (200 mL); displace with N2 and react at 80 °C for 4 h. After the reaction is completed, TLC is carried out with HEX / EA = 10 / 1 (V / V) as the eluent, and the target product is synthesized. After the reaction is completed, post-treatment is carried out; add (100 mL) + EA (30 mL) to extract the reaction, separate the layers to obtain the EA layer, concentrate, and separate by silica gel column chromatography (Hex / EA = 10 / 1 (V / V)) to obtain 2.9 g of a yellow solid (yield 13.51%, purity HPLC 99.64%). The 1H NMR data are as follows:

[0043] 1 1H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 2.0 Hz, 1H), 7.64 (s, 1H), 7.55 (s, 1H), 7.47 (s, 1H), 7.04 (d, J = 2.0 Hz, 1H), 1.42 (s, 9H), 1.36 (s, 9H).

[0044] Example 2: Synthesis of compound K

[0045]

[0046]

[0047] Synthesis of compound F

[0048] Take a 1000 ml three-necked flask, add compound D (10.0 g, 40 mmol, 1.0 eq.), compound E (11.7 g, 50 mmol, 1.25 eq.), Pd 132 (280 mg, 0.4 mmol, 1% eq.), K 2 CO 3(13.8 g, 100 mmol, 2.5 eq.) and toluene / ethanol / H 2 O (200 / 200 / 50 mL), under nitrogen protection, stirred at 90 °C for 12 h. After the reaction was completed, most of the reaction solution was first rotary evaporated, deionized water was added, and the mixture was extracted with dichloromethane three times. Then it was rotary evaporated and stirred with silica gel for column chromatography (Hex:EA = 10:1). Finally, 21.0 g of brown solid was obtained (yield 94.2%). The 1H NMR data are as follows:

[0049] 1 1H NMR (400 MHz, CDCl 3 ) δ 8.52 (s, 1H), 8.31 (d, J = 5.2 Hz, 1H), 8.16–8.07 (m, 2H), 7.46 (dd, J = 9.1, 2.6 Hz, 3H), 7.31 (s, 1H), 7.28 (s, 1H), 7.20 (dd, J = 5.3, 1.4 Hz, 1H), 7.08 (s, 1H), 4.03 (s, 3H).

[0050] Synthesis of Compound G

[0051] Take a 250 mL single-necked flask, add Compound F (2.0 g, 7.2 mmol, 1.0 eq.), pyridine hydrochloride (10 g, mass ratio 5), o-DCB (2 mL), under nitrogen protection, react at 180 °C for 3.5 h. After the reaction was completed, it was cooled to room temperature, water and dichloromethane were added and stirred for 30 min, then separated, and the organic layer was collected to obtain the crude product. The crude product was slurried with Hex to obtain a yellow solid (2.0 g, yield ~100%).

[0052] 1 1H NMR (400 MHz, DMSO) δ 11.22 (s, 1H), 8.15 (dd, J = 18.5, 7.7 Hz, 2H), 7.59–7.52 (m, 2H), 7.46–7.36 (m, 2H), 7.24 (t, J = 7.6 Hz, 1H), 7.20–7.13 (m, 1H), 6.67 (d, J = 1.2 Hz, 1H), 6.52 (dd, J = 6.7, 1.7 Hz, 1H).

[0053] Synthesis of Compound H

[0054] Take the above Compound G, add POCl 3 (10 mL) and o-DCB (1 mL), under nitrogen protection, react at 100 °C for 18 h. After the reaction was completed, it was cooled to room temperature. Rotary evaporate part of the POCl3 until it becomes viscous, then add ice water, stir thoroughly to quench POCl3, and then extract the reaction solution with dichloromethane to obtain the crude product. The crude product was slurried with Hex to obtain a yellow solid (2.0 g, yield ~100%). The 1H NMR data are as follows:

[0055] 1 H NMR (400 MHz, CDCl 3 ) δ 8.59 (s, 1H), 8.49 (dd, J = 5.1, 0.6 Hz, 1H), 8.14 (dd, J = 17.2, 7.5 Hz, 2H), 7.70–7.65 (m, 1H), 7.55 (dd, J = 5.1, 1.5 Hz, 1H), 7.53–7.42 (m, 3H), 7.35 (t, J = 7.6 Hz, 1H), 7.32–7.27 (m, 1H).

[0056] Synthesis of Compound J

[0057] Take a 250 ml single-necked flask, add the above-mentioned Compound H (2.0 g, 7.17 mmol, 1.0 eq.), add Compound I (11.7 g, 8.97 mmol, 1.25 eq.), Pd 132 (51 mg, 0.072 mmol, 1% eq.), K 2 CO 3 (2.48 g, 100 mmol, 2.5 eq.) and toluene / ethanol / H 2 O (50 / 50 / 10 ml), under nitrogen protection, stir and react at 90 °C for 12 h. After the reaction is completed, first evaporate most of the reaction solution, add deionized water, extract with dichloromethane three times, evaporate and stir through a silica gel column (Hex: EA = 10:1). Finally, 2.5 g of a brown solid is obtained (yield 89.3%). The hydrogen spectrum data are as follows:

[0058] 1 H NMR (400 MHz, CDCl3) δ 8.58 (d, J = 4.9 Hz, 1H), 8.15 (d, J = 12.7 Hz, 2H), 7.89–7.82 (m, 2H), 7.66 (t, J = 2.0 Hz, 1H), 7.54 (s, 1H), 7.50 (s, 1H), 7.38 (dd, J = 5.0, 1.0 Hz, 1H), 7.25 (d, J = 13.0 Hz, 2H), 7.20 (t, J = 2.0 Hz, 1H), 6.61 (t, J = 2.0 Hz, 1H), 4.29 (s, 2H), 1.36 (s, 9H).

[0059] Synthesis of Compound K

[0060] tert-Butyl nitrite (155 mg, 1 mmol) was added dropwise to a mixture of bis(pinacolato)diboron (127 mg, 0.5 mmol), compound J (195 mg, 0.5 mmol), and eosin Y (0.01 mmol) in acetonitrile (5 mL). The resulting mixture was stirred under blue LED irradiation at room temperature for 2 h (TLC). The mixture diluted with ethyl acetate (5 mL) was filtered through celite, and the filtrate was extracted with ethyl acetate (3 × 10 mL). The extract was washed with brine and dried over anhydrous Na 2 SO 4 and evaporated to give a crude product, which was purified by silica gel column chromatography (Hex:EA = 10:1) to afford 208 mg of a brown solid (yield 88%).

[0061] The data of hydrogen spectrum are as follows:

[0062] 1 H NMR (400 MHz, CDCl 3 ) δ 8.57 (d, J = 5.0 Hz, 1H), 8.15 (d, J = 12.7 Hz, 2H), 7.84 (d, J = 1.4 Hz, 2H), 7.67 (t, J = 1.9 Hz, 1H), 7.54 (s, 1H), 7.50 (s, 1H), 7.45 (dt, J = 8.1, 2.0 Hz, 2H), 7.38 (dd, J = 5.0, 1.0 Hz, 1H), 7.25 (d, J = 13.0 Hz, 2H), 1.38 (s, 12H), 1.34 (s, 9H).

[0063] Example 3: Synthesis of Complex 9

[0064]

[0065] Synthesis of Compound 9b

[0066] In a 250 ml three-necked flask, C (5.0 g, 12.4 mmol, 1.0 eq), 9a (11.81 g, 37.3 mmol, 3.0 eq), Cu (393 mg, 6.2 mmol 0.5 eq), CuI (1.18 g, 0.5 eq), 1,10-phenanthroline (2.23 g, 12.4 mmol, 1.0 eq), and cesium carbonate (12.1 g, 37.3 mmol, 3.0 eq) were added. 100 ml of anhydrous xylene was used as the reaction solvent. Under nitrogen protection, the reaction was carried out at an oil bath temperature of 160 °C for 72 h and then cooled to room temperature. The reaction solution was directly filtered with EA as the eluent to remove inorganic salts, and then silica gel column chromatography was carried out (chromatographic solution Hex:EA = 8:1). 3.2 g of a yellow fluorescent product spot was collected (yield 43.8%). The data of hydrogen spectrum are as follows:

[0067] 1 1H NMR (400 MHz, Chloroform-d) δ 7.71 (s, 1H), 7.69 (s, 1H), 7.66 (d, J = 2.0 Hz, 1H), 7.59 (s, 1H), 7.43 (t, J = 2.0 Hz, 1H), 7.18 (d, J = 2.0 Hz, 2H), 7.04 (d, J = 2.0 Hz, 1H), 1.42 (s, 9H), 1.36 (d, J = 1.5 Hz, 27H).

[0068] Synthesis of Compound 9c

[0069] Place a 250 mL single-necked flask, add 9b (3.0 g, 5.08 mmol, 1.0 eq), K (2.68 g, 5.34 mmol, 1.05 eq), Pd 132 (71 mg, 0.1 mmol, 0.02 eq), K 2 CO 3 (1.4 g, 10.16 mmol, 2.0 eq), and THF / water (80 mL / 16 mL). Under nitrogen protection, react at 70 °C for 12 h. After the reaction is completed, first rotary evaporate most of the solvent, add water, extract twice with EA, stir with silica gel and rotary evaporate, and pass through a silica gel column with (Hex:EA = 6:1) to obtain 3.6 g of a white solid with a yield of 80.2%. The 1H NMR data is as follows:

[0070] 1 1H NMR (400 MHz, Chloroform-d) δ 8.58 (d, J = 4.9 Hz, 1H), 8.15 (d, J = 12.7 Hz, 2H), 7.98 (t, J = 2.0 Hz, 1H), 7.88–7.77 (m, 3H), 7.72–7.64 (m, 2H), 7.61 (t, J = 2.0 Hz, 1H), 7.54 (d, J = 5.5 Hz, 2H), 7.50 (s, 1H), 7.43 (t, J = 2.0 Hz, 1H), 7.38 (dd, J = 5.0, 1.0 Hz, 1H), 7.31 (t, J = 1.9 Hz, 1H), 7.28–7.16 (m, 4H), 7.04 (d, J = 2.0 Hz, 1H), 1.42 (s, 9H), 1.36 (d, J = 1.4 Hz, 36H).

[0071] Synthesis of Compound 9d

[0072] In a 250 mL three-necked flask, 9c (3.5 g, 3.95 mmol, 1.0 eq), iodobenzene (2.42 g, 11.8 mmol, 3.0 eq), Cu (125 mg, 1.97 mmol, 0.5 eq), CuI (375 mg, 1.97 mmol, 0.5 eq), 1,10-phenanthroline (783 mg, 3.95 mmol, 1.0 eq) and cesium carbonate (3.86 g, 11.85 mmol, 3.0 eq) were added. 100 mL of anhydrous xylene was used as the reaction solvent. Under nitrogen protection, the reaction was carried out at an oil bath temperature of 160 °C for 72 h and then cooled to room temperature. The reaction solution was directly filtered with EA as the eluent to remove inorganic salts, and then silica gel column chromatography was carried out (chromatographic solution Hex:EA = 5:1). 1.66 g of yellow fluorescent product spots were collected (yield 43.8%). The 1H NMR data are as follows:

[0073] 1 H NMR(400MHz,Chloroform-d)δ7.71(s,1H),7.69(s,1H),7.66(d,J=2.0Hz,1H),7.59(s,1H),7.43(t,J=2.0Hz,1H),7.18(d,J=2.0Hz,2H),7.04(d,J=2.0Hz,1H),1.42(s,9H),1.36(d,J=1.5Hz,27H).

[0074] Synthesis of Complex 9

[0075] Compound 9d (1.44 g, 1.5 mmol, 1.0 eq.), KPtCl 4 (676 mg, 1.8 mmol, 1.2 eq.), TBAB (72.4 mg, 0.225 mmol, 0.15 eq.) and 80 mL of acetic acid were added. Under argon protection, the reaction was stirred at 130 °C for 48 h. After the reaction was completed, after the reaction solution was cooled, the two batches of reaction solutions were poured into 400 mL of deionized water together and stirred for 10 min. A large amount of solid precipitated. The solid was filtered to obtain a solid, and the solid was dissolved in dichloromethane and passed through a silica gel column twice (the first time: pure dichloromethane, the second time: n-hexane / dichloromethane / = 2 / 1 (V / V / )). 1.45 g of product was obtained. The obtained product was slurried with 20 mL of Hex, and finally 1.05 g of product was obtained, with a yield of 61.1% and a purity of 99.90%. The 1H NMR data are as follows:

[0076] 11H NMR (400 MHz, Chloroform-d) δ 8.20 (s, 1H), 8.13 (s, 1H), 8.06 (d, J = 1.4 Hz, 2H), 7.87 (s, 1H), 7.77 (d, J = 15.9 Hz, 2H), 7.69 (d, J = 12.6 Hz, 2H), 7.62 (s, 1H), 7.57 (s, 1H), 7.52–7.44 (m, 4H), 7.43–7.37 (m, 5H), 7.35 (s, 1H), 7.26 (s, 1H), 7.23 (d, J = 2.0 Hz, 2H), 7.05 (d, J = 2.0 Hz, 1H), 6.97 (s, 1H), 6.66 (s, 1H), 1.38 (s, 9H), 1.36 (d, J = 1.4 Hz, 36H).

[0077] Example 4: Synthesis of Complex 25

[0078]

[0079] Synthesis of Compound 25b

[0080] In a 250 ml three-necked flask, add C (5.0 g, 12.4 mmol, 1.0 eq), 25a (12.54 g, 37.3 mmol, 3.0 eq), Cu (393 mg, 6.2 mmol 0.5 eq), CuI (1.18 g, 0.5 eq), 1,10-phenanthroline (2.23 g, 12.4 mmol, 1.0 eq) and cesium carbonate (12.1 g, 37.3 mmol, 3.0 eq). Use 100 ml of anhydrous xylene as the reaction solvent, protect with nitrogen, react at an oil bath temperature of 160 °C for 72 h, then cool to room temperature. The reaction solution is directly filtered with EA as the eluent to remove inorganic salts, and then silica gel column chromatography is carried out (chromatographic solution Hex:EA = 8:1). 3.5 g of yellow fluorescent product spots are collected (yield 46.3%). The 1H NMR data are as follows:

[0081] 1 1H NMR (400 MHz, Chloroform-d) δ 7.70 (d, J = 7.1 Hz, 2H), 7.66 (d, J = 2.0 Hz, 1H), 7.59 (s, 1H), 7.53 (d, J = 7.5 Hz, 1H), 7.50–7.46 (m, 2H), 7.45–7.34 (m, 3H), 7.22 (dd, J = 7.5, 2.0 Hz, 1H), 7.12 (d, J = 2.0 Hz, 1H), 7.04 (d, J = 2.0 Hz, 1H). 1.42 (s, 9H), 1.35 (d, J = 7.7 Hz, 18H).

[0082] Synthesis of Compound 25c

[0083] Take a 250 mL single-necked flask and add 25b (3.3 g, 5.41 mmol, 1.0 eq), K (2.86 g, 5.68 mmol, 1.05 eq), Pd 132 (78.1 mg, 0.11 mmol, 0.02 eq), K 2 CO 3 (1.5 g, 10.82 mmol, 2.0 eq), and THF / water (80 mL / 16 mL). Under nitrogen protection, react at 70 °C for 12 h. After the reaction is completed, first rotary evaporate most of the solvent, add water, extract twice with EA, stir with silica gel and rotary evaporate, and pass through a silica gel column with (Hex:EA = 6:1) to obtain 3.8 g of a white solid with a yield of 77.5%. The 1H NMR data are as follows:

[0084] 1 1H NMR (400 MHz, Chloroform-d) δ 8.58 (d, J = 4.9 Hz, 1H), 8.15 (d, J = 12.7 Hz, 2H), 7.98 (t, J = 2.0 Hz, 1H), 7.89–7.82 (m, 2H), 7.79 (s, 1H), 7.66 (d, J = 2.0 Hz, 2H), 7.61 (t, J = 2.0 Hz, 1H), 7.56–7.51 (m, 3H), 7.50–7.46 (m, 3H), 7.45–7.34 (m, 4H), 7.31 (t, J = 1.9 Hz, 1H), 7.28–7.19 (m, 3H), 7.12 (d, J = 2.1 Hz, 1H), 7.04 (d, J = 2.0 Hz, 1H), 1.42 (s, 9H), 1.38–1.32 (m, 27H).

[0085] Synthesis of Compound 25d

[0086] In a 250 mL three-necked flask, add 25c (3.6 g, 3.97 mmol, 1.0 eq), iodobenzene (2.45 g, 12 mmol, 3.0 eq), Cu (127 mg, 2 mmol, 0.5 eq), CuI (380 mg, 2 mmol, 0.5 eq), 1,10-phenanthroline (793 mg, 4 mmol, 1.0 eq), and cesium carbonate (3.9 g, 12 mmol, 3.0 eq). Use 100 mL of anhydrous xylene as the reaction solvent. Under nitrogen protection, react at an oil bath temperature of 160 °C for 72 h and then cool to room temperature. The reaction solution is directly filtered with EA as the eluent to remove inorganic salts, and then subjected to silica gel column chromatography (eluent Hex:EA = 5:1). Collect 1.98 g of the yellow fluorescent product spot (yield 51.0%). The 1H NMR data are as follows:

[0087] 11H NMR (400 MHz, Chloroform-d) δ 8.58 (d, J = 4.9 Hz, 1H), 8.16 (d, J = 31.0 Hz, 2H), 7.98 (t, J = 2.0 Hz, 1H), 7.87–7.76 (m, 3H), 7.70–7.64 (m, 3H), 7.61 (t, J = 2.0 Hz, 1H), 7.58–7.51 (m, 3H), 7.51–7.44 (m, 4H), 7.43–7.34 (m, 8H), 7.31 (t, J = 1.9 Hz, 1H), 7.28–7.19 (m, 2H), 7.12 (d, J = 2.0 Hz, 1H), 7.04 (d, J = 2.0 Hz, 1H), 1.42 (s, 9H), 1.38–1.32 (m, 27H).

[0088] Synthesis of Complex 25

[0089] Charge Compound 25d (1.47 g, 1.5 mmol, 1.0 eq.), KPtCl 4 (676 mg, 1.8 mmol, 1.2 eq.), TBAB (72.4 mg, 0.225 mmol, 0.15 eq.) and 80 ml of acetic acid. Under the protection of argon, stir and react at 130 °C for 48 h. After the reaction is completed, wait for the reaction solution to cool, then pour the two batches of reaction solutions into 400 mL of deionized water together, stir for 10 min, a large amount of solid precipitates, filter to obtain the solid, dissolve the solid in dichloromethane, stir and pass through the silica gel column twice (the first time: pure dichloromethane, the second time: n-hexane / dichloromethane / = 2 / 1 (V / V / )), obtain 1.21 g of the product, add 20 ml of Hex to the obtained product for pulping, and finally obtain 0.93 g of the product, with a yield of 53.1% and a purity of 99.92%. The hydrogen spectrum data is as follows:

[0090] 1 1H NMR (400 MHz, Chloroform-d) δ 8.16 (d, J = 31.0 Hz, 2H), 8.06 (d, J = 1.4 Hz, 2H), 7.87 (s, 1H), 7.79 (s, 1H), 7.73–7.65 (m, 3H), 7.62 (s, 1H), 7.59–7.44 (m, 8H), 7.43–7.34 (m, 8H), 7.29–7.20 (m, 2H), 7.11 (d, J = 2.0 Hz, 1H), 7.05 (d, J = 2.0 Hz, 1H), 6.97 (s, 1H), 6.67 (s, 1H), 1.38 (s, 9H), 1.37–1.33 (m, 27H).

[0091] Example 5: Synthesis of Complex 125

[0092]

[0093] Synthesis of Compound 125b

[0094] In a 500 ml three-necked flask, 9c (5 g, 5.65 mmol, 1.0 eq), 125a (6.19 g, 16.9 mmol, 3.0 eq), Cu (179.4 mg, 2.82 mmol, 0.5 eq), CuI (535.8 mg, 2.82 mmol, 0.5 eq), 1,10-phenanthroline (1.12 g, 5.65 mmol, 1.0 eq) and cesium carbonate (5.52 g, 16.95 mmol, 3.0 eq) were added. 180 ml of anhydrous xylene was used as the reaction solvent. Under nitrogen protection, the reaction was carried out at an oil bath temperature of 160 °C for 72 h and then cooled to room temperature. The reaction solution was directly filtered with EA as the eluent to remove inorganic salts, and then silica gel column chromatography was carried out (eluent Hex:EA = 5:1). 3.15 g of a yellow fluorescent product spot was collected (yield 49.6%). The 1H NMR data are as follows:

[0095] 1 H NMR(400MHz,Chloroform-d)δ8.58(d,J=4.9Hz,1H),8.20(s,1H),8.13(s,1H),7.98(t,J=2.0Hz,1H),7.84(d,J=1.0Hz,1H),7.79(s,2H),7.75–7.65(m,5H),7.61(dd,J=4.3,2.3Hz,2H),7.56(d,J=9.1Hz,2H),7.45–7.33(m,4H),7.31(t,J=1.9Hz,1H),7.26(s,1H),7.22–7.16(m,3H),7.04(d,J=2.0Hz,1H),1.42(s,9H),1.39–1.32(m,54H).

[0096] Synthesis of Complex 125

[0097] Charge Compound 125b (3 g, 2.6 mmol, 1.0 eq.), KPtCl 4(1.2 g, 3.2 mmol, 1.2 eq.), TBAB (125.7 mg, 0.39 mmol, 0.15 eq.), and 200 mL of acetic acid. Under argon protection, the reaction was stirred at 130 °C for 48 h. After the reaction was completed, the reaction solution was cooled, and the two batches of reaction solutions were poured into 600 mL of deionized water together and stirred for 10 min. A large amount of solid precipitated. The solid was obtained by suction filtration, dissolved in dichloromethane, and passed through a silica gel column twice (the first time: pure dichloromethane, the second time: n - hexane / dichloromethane = 2 / 1 (V / V)). 2.6 g of the product was obtained. The obtained product was slurried with 20 mL of Hex, and finally 1.9 g of the product was obtained, with a yield of 55.6% and a purity of 99.89%. The 1H NMR data are as follows:

[0098] 1 H NMR (400 MHz, Chloroform - d) δ 8.20 (s, 1H), 8.13 (s, 1H), 8.06 (d, J = 1.4 Hz, 2H), 7.87 (s, 1H), 7.80–7.72 (m, 3H), 7.72–7.66 (m, 3H), 7.62 (s, 2H), 7.57 (s, 1H), 7.49 (d, J = 16.5 Hz, 2H), 7.44–7.34 (m, 4H), 7.29–7.18 (m, 4H), 7.05 (d, J = 2.0 Hz, 1H), 6.97 (s, 1H), 6.66 (s, 1H), 1.38 (s, 9H), 1.37 (s, 9H), 1.36 (d, J = 1.5 Hz, 36H), 1.34 (s, 9H).

[0099] Example 6: Synthesis of Complex 175

[0100]

[0101] Synthesis of Compound 175c

[0102] Take a 500 mL three - necked flask and add Compound 175a (5.0 g, 20.32 mmol, 1.0 eq.), Compound 175b (2.37 g, 21.3 mmol, 1.05 eq.), Pd 132 (14 mg, 0.02 mmol, 1% eq.), K 2 CO 3 (7.01 g, 50.8 mmol, 2.5 eq.) and toluene / ethanol / H 2O(100 / 100 / 20 ml), under nitrogen protection, stir the reaction at 90 °C for 12 h. After the reaction is completed, first rotary evaporate most of the reaction solution, add deionized water, extract with dichloromethane three times, rotary evaporate and stir with silica gel for column chromatography (Hex: EA = 10:1). Finally, 4.82 g of brown solid is obtained (yield 86.1%). The 1H NMR data are as follows:

[0103] 1 1H NMR (400 MHz, CDCl 3 ) δ 9.67 (s, 1H), 8.36 (d, J = 5.0 Hz, 1H), 8.15 (s, 1H), 7.66 (s, 1H), 7.59 (d, J = 1.0 Hz, 1H), 7.54 (s, 1H), 7.48 (d, J = 7.5 Hz, 3H), 7.35 (dd, J = 5.0, 1.0 Hz, 1H), 7.27 (d, J = 7.5 Hz, 3H).

[0104] Synthesis of Compound 175d

[0105] Take a 500 ml single-necked flask, add the above compound 175c (4.8 g, 17.2 mmol, 1.0 eq.), add compound I (4.1 g, 21.5 mmol, 1.25 eq.), Pd 132 (12.1 mg, 0.017 mmol, 1% eq.), K 2 2CO 3 (5.93 g, 43 mmol, 2.5 eq.) and toluene / ethanol / H 2 2O (100 / 100 / 20 ml), under nitrogen protection, stir the reaction at 90 °C for 12 h. After the reaction is completed, first rotary evaporate most of the reaction solution, add deionized water, extract with dichloromethane three times, rotary evaporate and stir with silica gel for column chromatography (Hex: EA = 10:1). Finally, 5.9 g of brown solid is obtained (yield 88.05%). The 1H NMR data are as follows:

[0106] 1 1H NMR (400 MHz, CDCl3) δ 9.67 (s, 1H), 8.59 (d, J = 5.0 Hz, 1H), 8.15 (s, 1H), 7.81 (d, J = 1.0 Hz, 1H), 7.69–7.64 (m, 2H), 7.54 (s, 1H), 7.48 (d, J = 7.5 Hz, 2H), 7.38 (dd, J = 5.0, 1.0 Hz, 1H), 7.27 (d, J = 7.5 Hz, 2H), 7.20 (t, J = 2.0 Hz, 1H), 6.61 (t, J = 2.0 Hz, 1H), 4.29 (s, 2H), 1.36 (s, 9H).

[0107] Synthesis of Compound 175e

[0108] tert-Butyl nitrite (1.56 g, 10 mmol) was added dropwise to a mixture of bis(pinacolato)diboron (1.3 g, 5 mmol), compound 175d (1.96 g, 5 mmol) and eosin Y (0.1 mmol) in acetonitrile (50 mL). The resulting mixture was stirred under blue LED irradiation at room temperature for 3 h (TLC). The mixture diluted with ethyl acetate (50 mL) was filtered through celite, and the filtrate was extracted with ethyl acetate (3 × 20 mL). The extract was washed with brine and dried over anhydrous Na 2 SO 4 and evaporated to give a crude product, which was purified by silica gel column chromatography (Hex:EA = 10:1) to afford 1.9 g of a brown solid (yield 76.1%).

[0109] The data of hydrogen spectrum are as follows:

[0110] 1 H NMR (400 MHz, CDCl 3 ) δ 9.67 (s, 1H), 8.59 (d, J = 5.0 Hz, 1H), 8.15 (s, 1H), 7.80 (d, J = 1.1 Hz, 1H), 7.69–7.65 (m, 2H), 7.54 (s, 1H), 7.51–7.42 (m, 4H), 7.38 (dd, J = 5.0, 1.0 Hz, 1H), 7.27 (d, J = 7.5 Hz, 2H), 1.38 (s, 12H), 1.34 (s, 9H).

[0111] Synthesis of compound 175f

[0112] A 250 mL single-necked flask was charged with 175e (3.8 g, 7.56 mmol, 1.0 eq), 9b (4.68 g, 7.94 mmol, 1.05 eq), Pd 132 (107.3 mg, 0.15 mmol, 0.02 eq), K 2 CO 3 (2 g, 14.52 mmol, 2.0 eq), and THF / water (100 mL / 20 mL). Under nitrogen protection, the reaction was carried out at 70 °C for 12 h. After the reaction was completed, most of the solvent was first evaporated, water was added, and the mixture was extracted twice with EA. The mixture was stirred with silica gel and evaporated, and then purified by silica gel column chromatography (Hex:EA = 6:1) to give 5.1 g of a white solid with a yield of 76.2%. The data of hydrogen spectrum are as follows:

[0113] 11H NMR (400 MHz, Chloroform-d) δ 9.67 (s, 1H), 8.59 (d, J = 5.0 Hz, 1H), 8.15 (s, 1H), 7.98 (t, J = 2.0 Hz, 1H), 7.83–7.77 (m, 2H), 7.71–7.64 (m, 3H), 7.61 (t, J = 2.0 Hz, 1H), 7.54 (d, J = 5.5 Hz, 2H), 7.48 (d, J = 7.5 Hz, 2H), 7.43 (t, J = 2.0 Hz, 1H), 7.38 (dd, J = 5.0, 1.0 Hz, 1H), 7.32–7.25 (m, 3H), 7.18 (d, J = 2.0 Hz, 2H), 7.04 (d, J = 2.0 Hz, 1H), 1.42 (s, 9H), 1.36 (d, J = 1.4 Hz, 36H).

[0114] Synthesis of 175 g of Compound

[0115] In a 250 ml three-necked flask, add 175f (5 g, 5.65 mmol, 1.0 eq), 3-iodobiphenyl (4.75 g, 16.9 mmol, 3.0 eq), Cu (179.4 mg, 2.83 mmol, 0.5 eq), CuI (538 mg, 2.83 mmol, 0.5 eq), 1,10-phenanthroline (1.12 g, 5.65 mmol, 1.0 eq) and cesium carbonate (5.51 g, 16.95 mmol, 3.0 eq). Use 150 ml of anhydrous xylene as the reaction solvent, protect with nitrogen, react at an oil bath temperature of 160 °C for 72 h, then cool to room temperature. Filter the reaction solution directly with EA as the eluent to remove inorganic salts, and then stir and perform silica gel column chromatography (chromatographic solution Hex:EA = 5:1). Collect 3.1 g of the yellow fluorescent product spot (yield 52.9%). The 1H NMR data is as follows:

[0116] 1 1H NMR (400 MHz, Chloroform-d) δ 8.59 (d, J = 5.0 Hz, 1H), 8.16 (s, 1H), 7.98 (t, J = 2.0 Hz, 1H), 7.83–7.77 (m, 3H), 7.73–7.64 (m, 5H), 7.63–7.57 (m, 3H), 7.55 (s, 1H), 7.48–7.30 (m, 12H), 7.27 (s, 1H), 7.18 (d, J = 2.0 Hz, 2H), 7.04 (d, J = 2.0 Hz, 1H), 1.42 (s, 9H), 1.36 (d, J = 1.4 Hz, 36H).

[0117] Synthesis of Complex 175

[0118] 175 g (3 g, 2.9 mmol, 1.0 eq.) of the input compound, KPtCl 4 (1.3 g, 3.48 mmol, 1.2 eq.), TBAB (140.2 mg, 0.435 mmol, 0.15 eq.) and 300 mL of acetic acid. Under argon protection, the reaction was stirred at 130 °C for 48 h. After the reaction was completed and the reaction solution was cooled, the two batches of reaction solutions were poured into 600 mL of deionized water together, stirred for 10 min, and a large amount of solid precipitated. The solid was obtained by suction filtration. The solid was dissolved in dichloromethane and passed through a silica gel column twice (the first time: pure dichloromethane, the second time: n-hexane / dichloromethane / = 2 / 1 (V / V / )), and 3.1 g of the product was obtained. 80 mL of Hex was added to the obtained product for slurrying, and finally 2.14 g of the product was obtained, with a yield of 61.1% and a purity of 99.90%. The 1H NMR data is as follows:

[0119] 1 H NMR (400 MHz, Chloroform-d) δ 8.16 (s, 1H), 8.06 (s, 1H), 7.96 (s, 1H), 7.87 (s, 1H), 7.79 (t, J = 2.0 Hz, 1H), 7.75 (s, 1H), 7.71 (s, 1H), 7.66 (d, J = 1.9 Hz, 3H), 7.64–7.57 (m, 3H), 7.50 (s, 1H), 7.48–7.34 (m, 8H), 7.32 (dt, J = 7.5, 2.1 Hz, 1H), 7.27 (d, J = 5.5 Hz, 2H), 7.23 (d, J = 2.0 Hz, 2H), 7.05 (d, J = 2.0 Hz, 1H), 6.98 (s, 1H), 1.38 (s, 9H), 1.36 (d, J = 1.4 Hz, 36H).

[0120] Example 7: Synthesis of Complex 190

[0121]

[0122] Synthesis of Compound 190b

[0123] Take a 250 mL single-necked flask and add A (10.0 g, 53 mmol, 1.0 eq.), 190a (6.6 g, 53 mmol, 1.0 eq.), Na 2 S 2 O 5(508 mg, 2.6 mmol, 0.05 eq), DMF (200 mL); Replace with N2 and react at 80 °C for 4 h. After the reaction is completed, TLC is carried out with HEX / EA = 10 / 1 (V / V) as the developing solvent. The target product is synthesized, the reaction is completed, and post-treatment is carried out; Add (100 mL) + EA (30 mL) to extract the reaction. After liquid separation, the EA layer is obtained, concentrated, and separated by silica gel column chromatography (Hex / EA = 10 / 1 (V / V)) to obtain 3.3 g of a yellow solid (yield 21.3%, purity by HPLC 99.52%). The 1H NMR data are as follows:

[0124] 1 H NMR (400 MHz, CDCl3) δ 8.45 (d, J = 5.1 Hz, 3H), 7.93 (d, J = 5.0 Hz, 1H), 7.64 (s, 1H), 7.55 (s, 1H), 7.47 (s, 1H).

[0125] Synthesis of Compound 190c

[0126] In a 250 mL three-necked flask, add 190b (5.0 g, 17.2 mmol, 1.0 eq), 9a (16.32 g, 51.6 mmol, 3.0 eq), Cu (546 mg, 8.6 mmol, 0.5 eq), CuI (1.64 g, 8.6 mmol, 0.5 eq), 1,10-phenanthroline (3.09 g, 17.2 mmol, 1.0 eq) and cesium carbonate (16.8 g, 51.6 mmol, 3.0 eq). Use 100 mL of anhydrous xylene as the reaction solvent, protect with nitrogen, react at an oil bath temperature of 160 °C for 72 h, then cool to room temperature. The reaction solution is directly filtered with EA as the eluent to remove inorganic salts, and then silica gel column chromatography is carried out (eluent Hex:EA = 8:1). 3.8 g of a yellow fluorescent product spot is collected (yield 46.1%). The 1H NMR data are as follows:

[0127] 1 H NMR (400 MHz, Chloroform-d) δ 8.44 (d, J = 4.1 Hz, 2H), 7.82 (d, J = 5.0 Hz, 1H), 7.70 (d, J = 9.5 Hz, 2H), 7.59 (s, 1H), 7.43 (t, J = 2.0 Hz, 1H), 7.18 (d, J = 2.0 Hz, 2H), 1.36 (s, 18H). Synthesis of Compound 190d

[0128] Take a 250 mL single-necked flask and add 190c (3.5 g, 7.32 mmol, 1.0 eq), K (3.86 g, 7.69 mmol, 1.05 eq), Pd 132 (106.5 mg, 0.15 mmol, 0.02 eq), K2 CO 3 (2.0 g, 14.64 mmol, 2.0 eq), and THF / water (120 ml / 30 ml), under nitrogen protection, reacted at 70 °C for 12 h. After the reaction, most of the solvent was first evaporated, water was added, and it was extracted twice with EA, stirred with silica gel and evaporated, and passed through a silica gel column with (Hex:EA = 6:1) to obtain 4.6 g of a white solid, with a yield of 81.4%. The 1H NMR data are as follows:

[0129] 1 H NMR (400 MHz, Chloroform-d) δ 8.58 (d, J = 4.9 Hz, 1H), 8.48–8.43 (m, 2H), 8.15 (d, J = 12.7 Hz, 2H), 7.98 (t, J = 2.0 Hz, 1H), 7.89–7.77 (m, 4H), 7.70 (s, 1H), 7.61 (t, J = 2.0 Hz, 1H), 7.54 (d, J = 5.5 Hz, 2H), 7.50 (s, 1H), 7.43 (t, J = 2.0 Hz, 1H), 7.38 (dd, J = 5.0, 1.0 Hz, 1H), 7.31 (t, J = 1.9 Hz, 1H), 7.25 (d, J = 13.0 Hz, 2H), 7.18 (d, J = 2.0 Hz, 2H), 1.36 (s, 27H).

[0130] Synthesis of Compound 190e

[0131] In a 250 ml three-necked flask, 190d (3.0 g, 3.90 mmol, 1.0 eq), 9a (3.7 g, 11.7 mmol, 3.0 eq), Cu (124 mg, 1.95 mmol, 0.5 eq), CuI (371 mg, 1.95 mmol, 0.5 eq), 1,10-phenanthroline (773 mg, 3.90 mmol, 1.0 eq) and cesium carbonate (3.81 g, 11.7 mmol, 3.0 eq) were added. 100 ml of anhydrous xylene was used as the reaction solvent. Under nitrogen protection, after reacting at an oil bath temperature of 160 °C for 72 h, it was cooled to room temperature. The reaction solution was directly filtered with EA as the eluent to remove inorganic salts, and then subjected to silica gel column chromatography (eluent Hex:EA = 5:1). The yellow fluorescent product spot of 2.72 g (yield 72.4%) was collected. The 1H NMR data are as follows:

[0132] 11H NMR (400 MHz, Chloroform-d) δ 8.58 (d, J = 4.9 Hz, 1H), 8.48–8.43 (m, 2H), 8.20 (s, 1H), 8.13 (s, 1H), 7.98 (t, J = 2.0 Hz, 1H), 7.86–7.77 (m, 4H), 7.69 (d, J = 8.1 Hz, 2H), 7.61 (t, J = 2.0 Hz, 1H), 7.56 (d, J = 9.2 Hz, 2H), 7.43 (t, J = 1.9 Hz, 2H), 7.40 (dd, J = 5.0, 1.0 Hz, 1H), 7.35 (s, 1H), 7.31 (t, J = 1.9 Hz, 1H), 7.26 (s, 1H), 7.20 (dd, J = 15.2, 2.0 Hz, 4H), 1.36 (s, 45H).

[0133] Synthesis of Complex 190

[0134] Add Compound 190e (2.5 g, 2.6 mmol, 1.0 eq.), KPtCl 4 (1.17 g, 3.12 mmol, 1.2 eq.), TBAB (125.7 mg, 0.39 mmol, 0.15 eq.) and 80 ml of acetic acid. Under argon protection, stir the reaction at 130 °C for 48 h. After the reaction is completed, wait for the reaction solution to cool, then pour the two batches of reaction solutions into 400 mL of deionized water together, stir for 10 min, a large amount of solid precipitates, filter to obtain the solid, dissolve the solid in dichloromethane, and pass through a silica gel column twice (the first time: pure dichloromethane, the second time: n-hexane / dichloromethane / = 2 / 1 (V / V / )), obtain 1.45 g of the product, add 20 ml of Hex to the obtained product for slurrying, and finally obtain 1.9 g of the product, with a yield of 63.2% and a purity of 99.90%. The 1H NMR data are as follows:

[0135] 1 1H NMR (400 MHz, Chloroform-d) δ 8.58 (d, J = 5.0 Hz, 1H), 8.27 (s, 1H), 8.20 (s, 1H), 8.13 (s, 1H), 8.06 (d, J = 1.4 Hz, 2H), 7.89–7.83 (m, 2H), 7.78 (d, J = 8.2 Hz, 2H), 7.69 (d, J = 12.6 Hz, 2H), 7.62 (s, 1H), 7.57 (s, 1H), 7.49 (d, J = 16.5 Hz, 2H), 7.43 (t, J = 1.9 Hz, 2H), 7.35 (s, 1H), 7.28–7.19 (m, 5H), 7.02 (s, 1H), 6.90 (s, 1H), 1.36 (s, 45H).

[0136] Those skilled in the art should be aware that the above preparation method is only an exemplary example, and those skilled in the art can obtain other compound structures of the present invention by improving it.

[0137] Example 8:

[0138] Under a nitrogen atmosphere, samples of about 5.0 mg of the fully dried platinum complexes 9, 25, 125, 17, and 190 were weighed separately. The heating scanning rate was set at 10 °C / min, and the scanning range was 25 - 800 °C. The measured thermal decomposition temperatures were 421, 449, 434, 412, and 424 °C (the temperature corresponding to a 0.5% weight loss), indicating that these complexes have very excellent thermal stability.

[0139] Example 9:

[0140] An organic light-emitting diode was prepared using the luminescent material of the complex of the present invention. The device structure is shown in Figure 1 .

[0141] First, the transparent conductive ITO glass substrate 10 (with the anode 20 on it) was successively washed with a detergent solution, deionized water, ethanol, acetone, and deionized water, and then treated with oxygen plasma for 30 seconds.

[0142] Then, 10 nm thick HATCN was evaporated on the ITO as the hole injection layer 30.

[0143] Then, the compound HT was evaporated to form a 40 nm thick hole transport layer 40.

[0144] Then, a 20 nm thick light-emitting layer 50 was evaporated on the hole transport layer. The light-emitting layer was composed of a mixture of platinum complex 9 (20%) and CBP (80%) by doping.

[0145] Then, 40 nm thick AlQ 3 was evaporated as the electron transport layer 60.

[0146] Finally, 1 nm LiF was evaporated as the electron injection layer 70 and 100 nm Al was evaporated as the device cathode 80.

[0147] Example 10:

[0148] The organic light-emitting diode was prepared using complex 25 to replace complex 9 by the method described in Example 8.

[0149] Example 11:

[0150] The organic light-emitting diode was prepared using complex 125 to replace complex 9 by the method described in Example 8.

[0151] Example 12:

[0152] Replace complex 9 with complex 175, and prepare an organic light-emitting diode by the method described in Example 8.

[0153] Example 13:

[0154] Replace complex 9 with complex 190, and prepare an organic light-emitting diode by the method described in Example 8.

[0155] Comparative Example 1:

[0156] Replace complex 9 with complex Ref-1 (CN107573383A), and prepare an organic light-emitting diode by the method described in Example 7.

[0157] Comparative Example 2:

[0158] Replace complex 9 with complex Ref-2 (CN107573383A), and prepare an organic light-emitting diode by the method described in Example 7.

[0159] HATCN, HT, AlQ in the device 3 , Ref-1, Ref-2 and the structural formula of CBP are as follows:

[0160]

[0161] The device performances of the organic electroluminescent devices in Example 5, Example 6, Example 7, Comparative Example 1, and Comparative Example 2 at a current density of 20 mA / cm 2 are listed in Table 1:

[0162] Table 1 Measurement of device performances of organic electroluminescent devices

[0163]

[0164] It can be seen from the data in Table 1 that under the same conditions, when the platinum complex material of the present invention is applied to an organic light-emitting diode, it has a lower driving voltage and a higher luminous efficiency. In addition, the device lifetime of the organic light-emitting diode based on the complex of the present invention is significantly better than that of the complex materials in the comparative examples, which can meet the requirements of the display industry for luminescent materials and has good industrialization prospects.

Claims

1. A platinum complex based on a carbazole-modified ONCN tetradentate ligand, which is a compound having the structure of formula (I): Wherein: X 1 to X 6 each independently selected from CR 0 ; X 11 to X 14 each independently selected from N or CR 0 ; X 7 to X 10 each independently selected from N, C or CR 0 ; R 0 and R 2 -R 4 each independently selected from the following groups: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 ring carbon atoms, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted alkoxy having 1-20 carbon atoms, substituted or unsubstituted aryl having 6-30 carbon atoms, or substituted or unsubstituted heteroaryl having 3-30 carbon atoms; R 1 is independently selected from the following groups: substituted or unsubstituted aryl having 6-30 carbon atoms, or substituted or unsubstituted heteroaryl having 3-30 carbon atoms; The substitution is by deuterium, halogen, cyano or C 1 -C 4 alkyl; The heteroatom in the heteroaryl group is one or more of N, S, and O.

2. The platinum complex according to claim 1, wherein, R 0 、R 2 -R 4 each independently selected from: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1-6 carbon atoms, substituted or unsubstituted cycloalkyl having 3-6 ring carbon atoms, substituted or unsubstituted alkenyl having 2-6 carbon atoms, substituted or unsubstituted alkoxy having 1-6 carbon atoms, substituted or unsubstituted aryl having 6-12 carbon atoms, or substituted or unsubstituted heteroaryl having 3-6 carbon atoms; R 1 is independently selected from the following groups: substituted or unsubstituted aryl having 6-12 carbon atoms, or substituted or unsubstituted heteroaryl having 3-6 carbon atoms.

3. The platinum complex according to claim 2, wherein, R 0 、R 2 -R 3 Each independently selected from: hydrogen, deuterium, halogen, C 1 -C 4 alkyl, cyano, substituted or unsubstituted cycloalkyl having 3-6 ring carbon atoms, substituted or unsubstituted aryl having 6-12 carbon atoms, or substituted or unsubstituted heteroaryl having 3-6 carbon atoms; R 4 R is selected from substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 6 carbon atoms 1 is selected from substituted or unsubstituted aryl having 6 to 12 carbon atoms, or substituted or unsubstituted heteroaryl having 3 to 6 carbon atoms.

4. The platinum complex according to claim 3, wherein, R 0 and R 2 -R 3 each independently selected from: hydrogen, deuterium, methyl, isopropyl, isobutyl, tert-butyl, cyano, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, or substituted or unsubstituted pyrimidinyl; R 4 selected from substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted quinolinyl, R 1 selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted quinolinyl.

5. The platinum complex according to any one of claims 1-4, wherein, X 1 to X 7 、X 9 -X 10 each independently is CR 0 ; X 8 is C, X 11 to X 14 each independently is CR 0 or N; and X 11 to X 14 only one of them is N.

6. The platinum complex according to claim 5, wherein, R 0 Each independently selected from: hydrogen, deuterium, methyl, isopropyl, isobutyl, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl; R 2 -R 3 Each independently selected from: hydrogen, deuterium, methyl, isopropyl, isobutyl, or tert-butyl; R 1 、R 4 Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl.

7. A platinum complex based on a carbazole-modified ONCN tetradentate ligand, which is one of the following structures:

8. A precursor of the platinum complex according to any one of claims 1-6, that is, a ligand, and the structural formula is as follows: where X 1 to X 14 ; R 0 -R 4 is defined as shown in any one of claims 1-6.

9. Use of the platinum complex according to any one of claims 1-7 in an organic optoelectronic device, and the organic optoelectronic device includes an organic light-emitting diode, an organic thin-film transistor, an organic photovoltaic device, a light-emitting electrochemical cell, and a chemical sensor.

10. An organic light-emitting diode, which includes a cathode, an anode, and an organic layer, and the organic layer is one or more of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer, and an electron transport layer; at least one of the hole injection layer, the hole transport layer, the hole blocking layer, the electron injection layer, the light-emitting layer, and the electron transport layer contains the platinum complex according to any one of claims 1-7.

11. The organic light-emitting diode according to claim 10, wherein the platinum complex is a light-emitting material in the light-emitting layer or an electron transport material in the electron transport layer.

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