Platinum complex luminescent material with NNCN tetradentate ligand and its application

Abstract

The present invention relates to a platinum complex luminescent material with an NNCN tetradentate ligand and its applications. The platinum complex is a compound having the structure of chemical formula (I). This compound is applied in an organic light-emitting diode, having a lower driving voltage and a higher luminous 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. The present invention also provides an organic electroluminescent device, comprising a cathode, an anode and an organic layer, wherein 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 transport layer, and an electron injection layer, and at least one layer of the organic layer contains the compound in structural formula (I).

Description

Technical Field

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

[0002] Organometallic complex luminescent materials are a new cross-research field developed after inorganic luminescent materials. Compared with inorganic luminescent materials, organometallic complex luminescent materials have the advantages of high luminescence efficiency, high brightness, wide viewing angle, fast response speed, etc. Among them, heavy metal complexes such as iridium (Ir) and platinum (Pt) with d6 and d8 electronic structures can generate strong spin-orbit coupling, increasing the intersystem crossing probability between singlet and triplet states, greatly improving the phosphorescence efficiency, shortening the phosphorescence lifetime, reducing phosphorescence quenching, and achieving phosphorescence at room temperature. The regulation of the emission color of OLEDs can be achieved through the structural design of luminescent materials. OLEDs can include one or more luminescent layers to achieve the required spectrum. Currently, green phosphorescent materials are the most mature type of materials. However, the development of deep red and blue materials lags far behind that of green materials due to factors such as their smaller energy gaps and mismatches with host materials respectively.

[0003] The research on red luminescent materials has become a bottleneck restricting the development of high-quality information display. The main reasons for this situation are: (1) The energy level difference of the compound corresponding to red light emission is small, which increases the difficulty in the design of ligands for red light materials; (2) In the red light material system, there is a strong π-π bond interaction or a strong charge transfer property, which will exacerbate the aggregation of molecules and easily lead to quenching; (3) The stability of red light materials is low. Therefore, by selecting a suitable red light material, the energy gap (Eg) is reduced, thereby reducing the energy required for the transition and causing a red shift.

[0004] At the same time, in order to meet the needs of industrialization, for red light material devices, their performance, such as luminescence efficiency and service life, still needs to be further improved. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the present invention provides a class of platinum complex luminescent materials with an NNCN tetradentate ligand, and this material has good luminescence efficiency when applied to organic light-emitting diodes.

[0006] The present invention also provides an organic light-emitting diode containing the platinum complex.

[0007] The platinum complex with an NNCN tetradentate ligand is a compound having the structure of formula (I):

[0008]

[0009] Wherein:

[0010] A 1 and A 3 is selected from the group consisting of R 0 substituted or unsubstituted N-heteroaryl containing 4 to 60 carbon atoms;

[0011] A 2 is selected from the group consisting of R 0 substituted or unsubstituted aryl having 6 to 60 carbon atoms, R 0 substituted or unsubstituted heteroaryl having 4 to 60 carbon atoms;

[0012] A 1 , A 2 , P 1 and the ring formed by the coordination bond with Pt is a six-membered ring;

[0013] P 1 , P 2 and the ring formed by the coordination bond with Pt is a five-membered ring;

[0014] P 2 , A 3 and the ring formed by the coordination bond with Pt is a five-membered ring;

[0015] R 0 -R 5 are each independently selected from the following groups: hydrogen, deuterium, halogen, amino, carbonyl, carboxyl, thioalkyl, cyano, sulfonyl, phosphino, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, or adjacent R 0 -R 5 groups can optionally be connected to form a ring; the substitution is by halogen, amino, cyano or C 1 -C 4 alkyl;

[0016] The heteroatoms in the heteroaryl are one or more of N, S, O.

[0017] Preferably, R 0 -R 5Each independently selected from: hydrogen, deuterium, halogen, amino group, thioalkyl group, cyano group, substituted or unsubstituted alkyl group having 1-6 carbon atoms, substituted or unsubstituted cycloalkyl group having 3-6 ring carbon atoms, substituted or unsubstituted alkenyl group having 2-6 carbon atoms, substituted or unsubstituted alkoxy group having 1-6 carbon atoms, substituted or unsubstituted aryl group having 6-12 carbon atoms, or substituted or unsubstituted heteroaryl group having 3-6 carbon atoms.

[0018] Preferably, R 0 -R 5 Each independently selected from: hydrogen, deuterium, halogen, C 1 -C 4 alkyl group, cyano group, substituted or unsubstituted cycloalkyl group having 3-6 ring carbon atoms, substituted or unsubstituted aryl group having 6-12 carbon atoms, substituted or unsubstituted heteroaryl group having 3-6 carbon atoms.

[0019] Preferably, R 0 -R 5 Each independently selected from: hydrogen, deuterium, methyl group, isopropyl group, isobutyl group, tert-butyl group, cyano group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted pyrimidinyl group.

[0020] Preferably, R 0 -R 5 Each independently selected from: hydrogen, deuterium, methyl group, tert-butyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted pyridyl group.

[0021] A 1 Selected from R 0 Substituted or unsubstituted N-containing heteroaryl group having 4-20 carbon atoms; wherein the bonding part with A 2 , Pt is a five-membered or six-membered N heterocycle. A 3 Selected from R 0 Substituted or unsubstituted N-containing heteroaryl group having 4-20 carbon atoms with one N or two Ns; wherein the bonding part with Pt is a five-membered or six-membered N heterocycle.

[0022] A 2 Selected from R 0 Substituted or unsubstituted aromatic group having 6-20 carbon atoms, R 0 Substituted or unsubstituted heteroaryl group having 4-20 carbon atoms.

[0023] A 2 Selected from R 0 Substituted or unsubstituted N-containing heteroaryl group having 4-12 carbon atoms; wherein the bonding part with A1 The key-linking part is a five- or six-membered N-heterocycle, and 2 the position linked to A1 in A is an N atom.

[0024] More preferably, A 1 is selected from the following groups, where the dotted line represents the bond at the position linked to A 2 (not limited to the structures listed in the following list):

[0025]

[0026]

[0027] A 2 is selected from the following groups, where the dotted line represents the bond at the position linked to A 1 (not limited to the structures listed in the following list):

[0028]

[0029] A 3 is selected from the following groups, where the dotted line represents the bond at the position linked to P 2 (not limited to the structures listed in the following list):

[0030]

[0031]

[0032] More preferably, the general formula (I) is the following structure (not limited to the structures listed in the following list):

[0033] The following are examples of platinum complexes according to the present invention, but not limited to the listed structures:

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] The precursor of the above metal complex, i.e., the ligand, has the following structural formula:

[0040]

[0041] 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.

[0042] 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).

[0043] Preferably, the layer where the platinum complex represented by formula (I) is located is the light-emitting layer or the electron transport layer.

[0044] 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.

[0045] The organic layer can form a thin film by evaporation or solution method.

[0046] A series of platinum complex luminescent materials disclosed by the present invention have good luminescent properties and can be used as luminescent materials in organic light-emitting diodes. Description of the Drawings

[0047] Figure 1 It is a structural diagram of the organic light-emitting diode device of the present invention.

[0048] 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. Detailed Embodiments

[0049] The present invention does not require the synthesis method of the materials. For a more detailed description of the present invention, the following examples are given, but not limited thereto. The raw materials used in the following synthesis are all commercially available products (2d, 2f, 10a, 20a, 20c, 98c, and 98e are ordered products) unless otherwise specified.

[0050] Example 1:

[0051] Synthesis of Complex 2

[0052]

[0053] Synthesis of Compound 2b:

[0054] Under nitrogen protection, 2a (10.0 g, 81.3 mmol, 1 eq), m-dibromobenzene (28.8 g, 122.0 mmol, 1.5 eq), tetrakis(triphenylphosphine)palladium(0) (1.39 g, 1.87 mmol, 0.02 eq), potassium carbonate solution (2 M, 101.6 mL, 2.5 eq) and toluene (500 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen three times. Subsequently, the reaction mixture was heated to reflux and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 14.9 g of a white solid with a yield of 76.5%.

[0055] 1 H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.1, 1.5 Hz, 1H), 7.97 (t, J = 1.9 Hz, 1H), 7.91 (ddd, J = 8.4, 1.8, 1.1 Hz, 1H), 7.72–7.63 (m, 2H), 7.55 (ddd, J = 8.1, 2.0, 1.3 Hz, 1H), 7.40–7.34 (m, 1H), 7.27–7.21 (m, 1H).

[0056] Synthesis of compound 2c:

[0057] 2b (14.0 g, 59.8 mmol, 1 eq), bis(pinacolato)diboron (22.78 g, 89.7 mmol, 1.5 eq), potassium acetate (17.6 g, 179.4 mmol, 3 eq), Pd(dppf) 2 Cl 2 (0.83 g, 1.19 mmol, 0.02 eq) and toluene (500 ml) were added to a flask. The mixture was stirred at room temperature for 30 minutes, then heated to 80 °C and stirred for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 10.92 g of a pale yellow oil with a yield of 65%.

[0058] 11H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.06 (t, J = 1.9 Hz, 1H), 7.74 (dddd, J = 14.6, 7.1, 2.0, 1.2 Hz, 2H), 7.71–7.63 (m, 2H), 7.45 (dd, J = 7.7, 7.1 Hz, 1H), 7.24 (ddd, J = 6.3, 4.0, 2.1 Hz, 1H), 1.24 (s, 12H).

[0059] Synthesis of Compound 2e:

[0060] Under nitrogen protection, 2c (10 g, 45.8 mmol, 1.5 e.q.), 2d (7.7 g, 30.6 mmol, 1 e.q.), tetrakis(triphenylphosphine)palladium(0) (0.7 g, 0.61 mmol, 0.02 e.q.), potassium carbonate solution (2 M, 45.9 mL, 3.0 e.q.) and toluene (250 mL) were added into a three-necked flask. The flask was evacuated and filled with nitrogen, and this process was repeated three times. Subsequently, the reaction mixture was heated to reflux and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 6.35 g of a white solid with a yield of 63.4%.

[0061] 1 1H NMR (500 MHz, Chloroform-d) δ 9.56 (s, 1H), 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.29–8.23 (m, 2H), 7.92 (ddd, J = 8.4, 1.8, 1.1 Hz, 1H), 7.89–7.81 (m, 2H), 7.72–7.61 (m, 3H), 7.24 (ddd, J = 6.6, 4.0, 1.8 Hz, 1H), 6.54 (d, J = 1.9 Hz, 1H). 1.36 (s, 9H).

[0062] Synthesis of Compound 2g:

[0063] Under nitrogen protection, (Boc) 2 O, (6.5 g, 29.9 mmol, 1.2 e.q.) and 4-(dimethylamino)pyridine (0.46 g, 3.73 mmol, 0.15 e.q.) were added to a solution of 2f (5.0 g, 24.9 mmol, 1 e.q.) in acetonitrile (50 mL). After the addition was completed, the mixture was stirred at room temperature for two hours. The solvent was removed under reduced pressure, and the residue was separated by silica gel column chromatography (Al 2 O 3) 7.15 g of colorless liquid was obtained with a yield of 95.0%.

[0064] 1 H NMR (500 MHz, Chloroform-d) δ 6.74 (d, J = 6.6 Hz, 1H), 5.83 (d, J = 6.8 Hz, 1H), 1.61 (s, 9H), 1.36 (s, 9H).

[0065] Synthesis of compound 2h:

[0066] 2e (5.0 g, 15.3 mmol, 1.0 e.q), 2g (6.9 g, 22.9 mmol, 1.5 e.q.), potassium carbonate (6.3 g, 45.9 mmol, 3 e.q.), Pd 2 (dba) 3 (0.18 g, 0.31 mmol, 0.02 e.q.) and Xphos (0.21 g, 0.31 mmol, 0.02 e.q.) were added to a flask containing toluene (250 ml). The temperature was raised to 80 °C and the mixture was stirred for 8 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residue was separated by silica gel column chromatography to obtain 4.0 g of a white solid with a yield of 47.8%.

[0067] 1 H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.26 (dd, J = 7.3, 1.8 Hz, 1H), 8.18 (t, J = 1.9 Hz, 1H), 7.95–7.80 (m, 3H), 7.72–7.63 (m, 2H), 7.59 (t, J = 8.6 Hz, 1H), 7.24 (ddd, J = 6.6, 4.0, 1.8 Hz, 1H), 6.20 (d, J = 6.8 Hz, 1H), 6.04 (d, J = 2.0 Hz, 1H), 5.94 (d, J = 6.8 Hz, 1H), 1.61 (s, 9H), 1.43 (s, 9H), 1.35 (s, 9H).

[0068] Synthesis of compound 2i:

[0069] Dissolve 2h (4.0 g, 7.3 mmol) in dichloromethane (200 ml), add hydrochloric acid (0.1 M) to adjust the pH to 1, stir for 30 min, and filter the solid. The obtained solid is slurried with methanol, filtered, potassium carbonate (0.2 M) is added to adjust the pH to 7 - 8, and extracted with ethyl acetate. The organic phase is concentrated to obtain 3.0 g of a pale yellow solid with a yield of 91.7%.

[0070] 1 H NMR (500 MHz, Chloroform - d) δ 8.78 (dd, J=4.1, 1.6 Hz, 1H), 8.41 (s, 1H), 8.28 (dd, J=7.4, 1.9 Hz, 1H), 8.18 (t, J=1.9 Hz, 1H), 7.92 (ddd, J=8.6, 1.9, 1.2 Hz, 1H), 7.89–7.83 (m, 2H), 7.72–7.63 (m, 2H), 7.59 (t, J=8.6 Hz, 1H), 7.24 (ddd, J=6.6, 4.0, 1.8 Hz, 1H), 6.92 (d, J=6.4 Hz, 1H), 6.38 (d, J=6.4 Hz, 1H), 6.01 (d, J=1.9 Hz, 1H), 1.43 (s, 9H), 1.34 (s, 9H).

[0071] Synthesis of Complex 2:

[0072] Take a 250 mL single - necked flask, dissolve 2i (2.5 g, 5.57 mmol, 1 e.q.), potassium chloroplatinate (2.51 g, 6.68 mmol, 1.2 e.q.), and tetrabutylammonium bromide (50 mg) in acetic acid (250 mL). Under nitrogen protection, stir and react at 135 °C for 24 hours. After cooling to room temperature, water is added to the reaction solution to precipitate a solid, and the crude product is obtained by filtration. Recrystallization from dichloromethane / n - hexane (1 / 1) gives 2.0 g of an orange - red powder with a yield of 56%.

[0073] 1 H NMR (500 MHz, Chloroform - d) δ 8.94 (dd, J=5.3, 1.5 Hz, 1H), 7.93–7.84 (m, 2H), 7.77 (dd, J=7.6, 1.9 Hz, 1H), 7.63–7.53 (m, 3H), 7.41 (t, J=7.9 Hz, 1H), 7.26 (ddd, J=7.7, 5.5, 1.4 Hz, 1H), 6.40 (d, J=5.7 Hz, 1H), 6.14 (d, J=5.7 Hz, 1H), 5.64 (d, J=2.0 Hz, 1H), 1.45 (s, 9H), 1.37 (s, 9H).

[0074] 1313C NMR(125MHz,Common NMR Solvents)δ151.43,150.99,147.23,143.92,143.42,142.57,140.70,134.03,132.32,132.28,131.83,130.22,127.24,127.22,126.37,124.61,123.55,117.74,109.83,108.81,100.58,40.49,40.20,30.02,30.01,30.00,29.87.

[0075] ESI-HRMS(m / z):642.212(M+1).

[0076] Example 2:

[0077] Synthesis of Complex 10

[0078]

[0079] Synthesis of Compound 10b

[0080] Under nitrogen protection, 10a (8 g, 40.5 mmol, 1 e.q.), 2c (17.1 g, 60.7 mmol, 1.5 e.q.), tetrakis(triphenylphosphine)palladium(0) (0.93 g, 0.81 mmol, 0.02 e.q.), potassium carbonate solution (2 M, 60.7 mL, 3.0 e.q.) and toluene (300 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this was repeated three times. Subsequently, the reaction mixture was heated to 80 °C and refluxed with stirring overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 8.41 g of a white solid with a yield of 64.6%.

[0081] 1 1H NMR(500MHz,Chloroform-d)δ8.78(dd,J = 4.1,1.6Hz,1H),8.37(d,J = 8.0Hz,1H),8.27(t,J = 2.0Hz,1H),8.12–8.06(m,1H),7.92(ddd,J = 8.4,1.8,1.1Hz,1H),7.89–7.83(m,2H),7.72–7.61(m,3H),7.49(dd,J = 7.5,2.0Hz,1H),7.37(td,J = 7.4,1.3Hz,1H),7.28–7.21(m,2H).

[0082] Synthesis of Compound 10c

[0083] 10b (8.0 g, 24.9 mmol, 1.0 e.q), 2 g (11.3 g, 37.35 mmol, 1.5 e.q.), potassium carbonate (10.3 g, 74.7 mmol, 3 e.q.), Pd 2 (dba) 3 (0.29 g, 0.50 mmol, 0.02 e.q.) and Xphos (0.33 g, 0.50 mmol, 0.02 e.q.) were added to toluene (250 ml) in a flask. The temperature was raised to 80 °C and the mixture was stirred for 8 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residue was separated by silica gel column chromatography to give 6.2 g of a white solid with a yield of 46.2%.

[0084] 1 1H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.45 (d, J = 7.6 Hz, 1H), 8.18 (t, J = 2.0 Hz, 1H), 8.12 (dd, J = 7.7, 1.2 Hz, 1H), 7.92 (ddd, J = 8.6, 1.9, 1.2 Hz, 1H), 7.89–7.83 (m, 2H), 7.72–7.63 (m, 3H), 7.59 (t, J = 8.6 Hz, 1H), 7.41–7.34 (m, 1H), 7.32–7.21 (m, 2H), 6.30 (d, J = 6.8 Hz, 1H), 5.97 (d, J = 6.8 Hz, 1H), 1.61 (s, 9H), 1.35 (s, 9H).

[0085] Synthesis of compound 10d:

[0086] 10c (6.0 g, 11.1 mmol) was dissolved in dichloromethane (250 ml), and hydrochloric acid (0.1 M) was added to adjust the pH to 1. The mixture was stirred for 30 min and the solid was filtered. The obtained solid was slurried with methanol, filtered, potassium carbonate (0.2 M) was added to adjust the pH to 7 - 8, and the mixture was extracted with ethyl acetate. The organic phase was concentrated to give 4.89 g of a pale yellow solid with a yield of 89.4%.

[0087] 11H NMR (500 MHz, Chloroform-d) δ 9.70 (s, 1H), 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.47 (d, J = 7.6 Hz, 1H), 8.20–8.14 (m, 2H), 7.95–7.84 (m, 3H), 7.72–7.63 (m, 3H), 7.59 (t, J = 8.6 Hz, 1H), 7.41–7.35 (m, 1H), 7.29 (ddd, J = 8.2, 7.1, 1.3 Hz, 1H), 7.24 (ddd, J = 6.6, 4.0, 1.8 Hz, 1H), 7.02 (d, J = 6.4 Hz, 1H), 6.40 (d, J = 6.2 Hz, 1H), 1.34 (s, 9H).

[0088] Synthesis of Complex 10

[0089] Take a 250 mL single-necked flask, dissolve 10d (4.50 g, 10.2 mmol, 1 e.q.), potassium chloroplatinate (4.60 g, 12.24 mmol, 1.2 e.q.) and tetrabutylammonium bromide (90 mg) in acetic acid (150 mL). Under nitrogen protection, stir and react at 135 °C for 24 hours. After cooling to room temperature, add water to the reaction solution to precipitate a solid, and filter to obtain the crude product. Recrystallize with dichloromethane / n-hexane (1 / 1) to obtain 3.31 g of orange-red powder, with a yield of 51%.

[0090] 1 1H NMR (500 MHz, Chloroform-d) δ 8.98–8.93 (m, 1H), 8.09–8.04 (m, 1H), 7.96 (d, J = 7.8 Hz, 1H), 7.93–7.87 (m, 2H), 7.71 (dd, J = 6.2, 1.5 Hz, 1H), 7.63–7.53 (m, 3H), 7.41 (t, J = 7.9 Hz, 1H), 7.37–7.23 (m, 3H), 6.84 (d, J = 5.7 Hz, 1H), 6.17 (d, J = 5.7 Hz, 1H), 1.37 (s, 9H).

[0091] 1313C NMR (125 MHz, Common NMR Solvents) δ 151.43, 151.23, 147.23, 143.94, 142.67, 136.92, 135.82, 134.57, 134.05, 132.32, 132.28, 129.55, 127.24, 127.22, 127.14, 124.61, 123.75, 123.55, 121.33, 119.84, 115.88, 110.19, 109.05, 100.37, 40.20, 29.87.

[0092] ESI-HRMS (m / z): 636.165 (M+1).

[0093] Example 3:

[0094] Synthesis of Complex 20

[0095]

[0096]

[0097] Synthesis of Compound 20b

[0098] Under nitrogen protection, (Boc) 2 O, (13.37 g, 61.2 mmol, 1.2 e.q.) and 4-(dimethylamino)pyridine (0.93 g, 7.65 mmol, 0.15 e.q.) were added to a solution of 20a (10.0 g, 51.0 mmol, 1.0 e.q.) in acetonitrile (200 mL). After the addition was completed, the mixture was stirred at room temperature for two hours. The solvent was removed by distillation under reduced pressure, and the residue was separated by silica gel column chromatography (Al 2 O 3 ), to obtain 14.1 g of a colorless liquid with a yield of 93.1%.

[0099] 1 1H NMR (500 MHz, Chloroform-d) δ 7.94–7.88 (m, 2H), 7.49 (ddd, J = 8.4, 6.6, 1.0 Hz, 1H), 7.14 (td, J = 6.8, 1.3 Hz, 1H), 6.50 (d, J = 1.9 Hz, 1H), 1.61 (s, 9H).

[0100] Synthesis of Compound 20d

[0101] Under nitrogen protection, 20c (5 g, 16.5 mmol, 1 eq), 2c (6.95 g, 24.7 mmol, 1.5 eq), tetrakis(triphenylphosphine)palladium(0) (0.38 g, 0.33 mmol, 0.02 eq), potassium carbonate solution (2 M, 24.7 mL, 3.0 eq) and toluene (200 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this process was repeated three times. Subsequently, the reaction mixture was heated to reflux and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 3.86 g of a white solid with a yield of 62%.

[0102] 1 H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.39 (d, J = 8.0 Hz, 1H), 8.27 (t, J = 1.9 Hz, 1H), 8.16 (dt, J = 1.6, 0.8 Hz, 1H), 7.95–7.84 (m, 3H), 7.72–7.61 (m, 3H), 7.38–7.31 (m, 2H), 7.24 (ddd, J = 6.6, 4.0, 1.8 Hz, 1H), 1.35 (s, 9H).

[0103] Synthesis of Compound 20e

[0104] 20d (3.5 g, 9.27 mmol, 1 eq), 20b (4.12 g, 13.9 mmol, 1.5 eq), potassium carbonate (3.84 g, 27.8 mmol, 3 eq), Pd 2 (dba) 3 (0.11 g, 0.19 mmol, 0.02 eq) and Xphos (0.12 g, 0.19 mmol, 0.02 eq) were added to toluene (150 ml) in a flask. The temperature was raised to 80 °C and the reaction was stirred for 8 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 2.5 g of a white solid with a yield of 45.6%.

[0105] 11H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.45 (d, J = 7.6 Hz, 1H), 8.18 (t, J = 1.9 Hz, 1H), 8.07 (d, J = 2.1 Hz, 1H), 7.95–7.84 (m, 5H), 7.72–7.64 (m, 2H), 7.62 (d, J = 7.7 Hz, 1H), 7.59 (t, J = 8.6 Hz, 1H), 7.55–7.48 (m, 1H), 7.29–7.21 (m, 3H), 7.16 (td, J = 6.6, 1.3 Hz, 1H), 1.61 (s, 9H), 1.35 (s, 9H).

[0106] Synthesis of Compound 20f

[0107] Dissolve 20e (2.0 g, 3.77 mmol) in dichloromethane (100 ml), adjust the pH to 1 with hydrochloric acid (0.1 M), stir for 30 min, and filter the solid. The obtained solid is slurried with methanol, filtered, the pH is adjusted to 7 - 8 with potassium carbonate (0.2 M), and extracted with ethyl acetate. The organic phase is concentrated to obtain 1.67 g of a pale yellow solid with a yield of 89.8%.

[0108] 1 1H NMR (500 MHz, Chloroform-d) δ 9.69 (s, 1H), 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.48 (d, J = 7.4 Hz, 1H), 8.18 (t, J = 1.9 Hz, 1H), 8.11 (d, J = 1.8 Hz, 1H), 7.95–7.89 (m, 2H), 7.87 (ddd, J = 8.6, 1.9, 1.2 Hz, 1H), 7.72–7.64 (m, 2H), 7.64–7.53 (m, 4H), 7.36 (dd, J = 8.0, 1.4 Hz, 1H), 7.30–7.21 (m, 2H), 7.14 (dtd, J = 24.5, 7.2, 1.3 Hz, 2H), 1.35 (s, 9H).

[0109] Synthesis of Complex 20

[0110] Take a 250 mL single-necked flask, dissolve 20f (1.5 g, 3.0 mmol), potassium chloroplatinate (1.37 g, 3.6 mmol) and tetrabutylammonium bromide (50 mg) in acetic acid (150 mL). Under nitrogen protection, stir and react at 135 °C for 24 hours. After cooling to room temperature, add water to the reaction solution to precipitate a solid, and filter to obtain the crude product. Recrystallize from dichloromethane / n-hexane (1 / 1) to obtain 1.05 g of an orange-red powder with a yield of 51.1%.

[0111] 1 1H NMR (500 MHz, Chloroform-d) δ 8.98 (dd, J = 5.2, 1.4 Hz, 1H), 8.19 (d, J = 8.0 Hz, 1H), 7.94–7.82 (m, 5H), 7.68–7.62 (m, 2H), 7.62–7.53 (m, 3H), 7.41 (t, J = 7.9 Hz, 1H), 7.24–7.18 (m, 3H), 7.15 (td, J = 7.0, 1.6 Hz, 1H), 1.35 (s, 9H).

[0112] 13 13C NMR (125 MHz, Common NMR Solvents) δ 151.46, 147.52, 147.27, 145.45, 145.17, 142.96, 141.57, 137.20, 134.82, 134.27, 132.52, 132.32, 129.48, 128.24, 127.28, 127.24, 127.22, 124.79, 124.61, 123.55, 123.21, 121.96, 121.93, 121.79, 117.50, 115.89, 111.84, 109.18, 96.22, 35.99, 31.08.

[0113] ESI-HRMS (m / z): 686.681 (M+1).

[0114] Example 4:

[0115] Synthesis of Complex 44

[0116]

[0117] Synthesis of Compound 44c:

[0118] Under nitrogen protection, 44a (10.0 g, 42.7 mmol, 1 e.q.), 44b (13.98 g, 51.2 mmol, 1.2 e.q.), tetrakis(triphenylphosphine)palladium(0) (0.99 g, 0.85 mmol, 0.02 e.q.), potassium carbonate solution (2 M, 53.4 mL, 2.5 e.q.) and tetrahydrofuran (250 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this process was repeated three times. Subsequently, the reaction mixture was heated to 60 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 9.23 g of a white solid with a yield of 64.5%.

[0119] 1 H NMR (500 MHz, Chloroform-d) δ 7.59 (d, J = 2.1 Hz, 2H), 7.50 (t, J = 2.2 Hz, 1H), 7.43 (t, J = 2.2 Hz, 1H), 7.33 (s, 2H), 1.35 (s, 18H).

[0120] Synthesis of Compound 44d:

[0121] Under nitrogen protection, 2a (2.75 g, 22.4 mmol, 1 e.q.), 44c (9 g, 26.8 mmol, 1.2 e.q.), tetrakis(triphenylphosphine)palladium(0) (0.52 g, 0.45 mmol, 0.02 e.q.), potassium carbonate solution (2 M, 28 mL, 2.5 e.q.) and tetrahydrofuran (140 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this was repeated three times. Subsequently, the reaction mixture was heated to 60 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 5.24 g of a white solid with a yield of 62%.

[0122] 1 H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.0, 1.6 Hz, 1H), 7.94 (t, J = 2.1 Hz, 1H), 7.78 (t, J = 2.2 Hz, 1H), 7.73 (dd, J = 7.4, 1.5 Hz, 1H), 7.70–7.63 (m, 2H), 7.50 (t, J = 2.2 Hz, 1H), 7.38 (s, 2H), 7.24 (ddd, J = 7.1, 4.0, 1.6 Hz, 1H), 1.35 (s, 18H).

[0123] Synthesis of Compound 44e:

[0124] 44d (5.0 g, 13.2 mmol, 1 e.q), bis(pinacolato)diboron (5.03 g, 19.8 mmol, 1.5 e.q.), potassium acetate (5.46 g, 39.6 mmol, 3 e.q.), Pd(dppf) 2 Cl 2(0.19 g, 0.26 mmol, 0.02 e.q.) and toluene (200 mL) were added to a flask. The mixture was stirred at room temperature for 30 minutes, then heated to 80 °C and stirred for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residue was separated by silica gel column chromatography to obtain 3.67 g of a pale yellow oil, with a yield of 59.3%.

[0125] 1 H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.0, 1.6 Hz, 1H), 8.02 (t, J = 2.1 Hz, 1H), 7.86 (t, J = 2.2 Hz, 1H), 7.82 (t, J = 2.2 Hz, 1H), 7.73 (dd, J = 7.3, 1.6 Hz, 1H), 7.66 (td, J = 7.3, 1.7 Hz, 1H), 7.50 (t, J = 2.2 Hz, 1H), 7.37 (d, J = 2.2 Hz, 2H), 7.24 (ddd, J = 7.1, 4.1, 1.6 Hz, 1H), 1.35 (s, 18H), 1.24 (s, 12H).

[0126] Synthesis of compound 44f:

[0127] Under nitrogen protection, 10a (1.53 g, 6.21 mmol, 1 e.q.), 44e (3.5 g, 7.45 mmol, 1.2 e.q.), tetrakis(triphenylphosphine)palladium(0) (0.035 g, 0.31 mmol, 0.02 e.q.), potassium carbonate solution (2 M, 7.7 mL, 2.5 e.q.) and tetrahydrofuran (50 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this was repeated three times. Subsequently, the reaction mixture was heated to 60 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 2.12 g of a white solid, with a yield of 67.0%.

[0128] 11H NMR (500 MHz, Chloroform-d) δ 8.78 (dd, J = 4.0, 1.6 Hz, 1H), 8.38 (d, J = 8.0 Hz, 1H), 8.18 (t, J = 2.2 Hz, 1H), 8.12–8.06 (m, 1H), 7.98 (t, J = 2.2 Hz, 1H), 7.94 (t, J = 2.2 Hz, 1H), 7.84 (d, J = 7.9 Hz, 1H), 7.73 (dd, J = 7.4, 1.4 Hz, 1H), 7.67 (td, J = 7.3, 1.7 Hz, 1H), 7.52–7.46 (m, 2H), 7.43 (d, J = 2.1 Hz, 2H), 7.37 (td, J = 7.4, 1.3 Hz, 1H), 7.28–7.21 (m, 2H), 1.35 (s, 18H).

[0129] Synthesis of Compound 44g:

[0130] 44f (2 g, 3.92 mmol, 1. e.q), 20b (1.74 g, 5.89 mmol, 1.5 e.q.), potassium carbonate (1.62 g, 11.76 mmol, 3 e.q.), Pd 2 (dba) 3 (0.045 g, 0.078 mmol, 0.02 e.q.) and Xphos (0.037 g, 0.078 mmol, 0.02 e.q.) were added to a flask containing toluene (100 ml). The temperature was raised to 80 °C and the mixture was stirred for 8 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 1.14 g of a white solid with a yield of 54.3%.

[0131] Synthesis of Compound 44h:

[0132] 44g (1.0 g, 1.86 mmol) was dissolved in dichloromethane (50 ml), and the pH was adjusted to 1 with hydrochloric acid (0.1 M). The mixture was stirred for 30 min and the solid was filtered. The obtained solid was slurried with methanol, filtered, and the pH was adjusted to 7 - 8 with potassium carbonate (0.2 M). The mixture was extracted with ethyl acetate. The organic phase was concentrated to obtain 0.78 g of a pale yellow solid with a yield of 95.6%.

[0133] 11H NMR (500 MHz, Chloroform-d) δ 9.71 (s, 1H), 8.78 (dd, J = 4.1, 1.6 Hz, 1H), 8.48 (d, J = 7.5 Hz, 1H), 8.21–8.16 (m, 2H), 7.92 (ddd, J = 8.6, 1.9, 1.2 Hz, 1H), 7.91–7.84 (m, 2H), 7.72–7.63 (m, 3H), 7.62–7.54 (m, 2H), 7.55 (d, J = 1.9 Hz, 1H), 7.42–7.34 (m, 2H), 7.29 (ddd, J = 8.3, 7.1, 1.3 Hz, 1H), 7.24 (ddd, J = 6.6, 4.0, 1.8 Hz, 1H), 7.20–7.09 (m, 2H).

[0134] Synthesis of Complex 44

[0135] Take a 250 mL single-necked flask, dissolve 44h (0.6 g, 1.37 mmol, 1 e.q.), potassium chloroplatinate (0.68 g, 1.65 mmol, 1.2 e.q.) and tetrabutylammonium bromide (50 mg) in acetic acid (150 mL). Under nitrogen protection, stir and react at 135 °C for 24 hours. After cooling to room temperature, add water to the reaction solution to precipitate a solid, and filter to obtain the crude product. Recrystallize with dichloromethane / n-hexane (1 / 1) to obtain 0.68 g of orange-red powder, with a yield of 61.1%.

[0136] 1 1H NMR (500 MHz, Chloroform-d) δ 9.04–8.99 (m, 1H), 8.92–8.85 (m, 2H), 8.07 (dd, J = 7.8, 1.4 Hz, 1H), 7.98 (d, J = 7.9 Hz, 1H), 7.94–7.82 (m, 4H), 7.70 (dd, J = 6.2, 1.5 Hz, 1H), 7.65 (d, J = 1.8 Hz, 1H), 7.61 (td, J = 7.7, 1.3 Hz, 1H), 7.50 (t, J = 2.1 Hz, 1H), 7.46 (d, J = 2.1 Hz, 2H), 7.37–7.26 (m, 2H), 7.26–7.19 (m, 2H), 7.15 (s, 1H), 1.35 (s, 18H).

[0137] 1313C NMR (125 MHz, Common NMR Solvents) δ 151.61, 151.39, 146.36, 145.17, 144.49, 141.94, 141.55, 140.21, 138.95, 138.62, 137.58, 135.86, 134.94, 132.33, 129.58, 129.48, 127.69, 127.65, 127.25, 127.23, 127.07, 123.93, 123.91, 123.71, 122.60, 121.96, 121.93, 121.79, 121.33, 119.84, 116.12, 111.84, 110.52, 96.22, 34.96, 31.29.

[0138] ESI-HRMS (m / z): 818.883 (M+1).

[0139] Example 5:

[0140] Synthesis of Complex 98

[0141]

[0142] Synthesis of Compound 98b

[0143] 98a (10.0 g, 34.2 mmol, 1.0 e.q), bis(pinacolato)diboron (26.09 g, 102.7 mmol, 3.0 e.q.), potassium acetate (10.1 g, 102.7 mmol, 3.0 e.q.), Pd(dppf) 2 Cl 2 (0.5 g, 0.68 mmol, 0.02 e.q.) and toluene (500 mL) were added to a flask. Stirred at room temperature for 30 minutes, then heated to 80 °C and stirred for 10 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to give 8.1 g of a white powder with a yield of 61.1%.

[0144] 1 1H NMR (500 MHz, Chloroform-d) δ 7.75 (t, J = 2.2 Hz, 1H), 7.56 (d, J = 2.2 Hz, 2H), 1.35 (s, 9H), 1.24 (s, 24H).

[0145] Synthesis of Compound 98d

[0146] Under nitrogen protection, 98c (3.77 g, 13.8 mmol, 1 eq.), 98b (8 g, 20.7 mmol, 1.5 eq.), tetrakis(triphenylphosphine)palladium(0) (0.32 g, 0.28 mmol, 0.02 eq.), potassium carbonate solution (2 M, 20.7 mL, 3 eq.) and toluene (200 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this process was repeated three times. Subsequently, the reaction mixture was heated to 60 °C for reaction and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 3.9 g of a white solid with a yield of 63.2%.

[0147] 1 H NMR (500 MHz, Chloroform-d) δ 7.98 (t, J = 2.2 Hz, 1H), 7.90–7.83 (m, 1H), 7.74–7.67 (m, 1H), 7.59 (t, J = 2.1 Hz, 1H), 7.54 (t, J = 2.1 Hz, 1H), 7.51–7.44 (m, 2H), 7.44–7.37 (m, 3H), 7.33–7.28 (m, 2H), 1.35 (s, 9H), 1.24 (s, 12H).

[0148] Synthesis of Compound 98f

[0149] Under nitrogen protection, 98e (2.3 g, 7.6 mmol, 1 eq.), 98d (3.8 g, 8.4 mmol, 1.1 eq.), tetrakis(triphenylphosphine)palladium(0) (0.17 g, 0.15 mmol, 0.02 eq.), potassium carbonate solution (2 M, 11.4 mL, 3 eq.) and toluene (60 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this process was repeated three times. Subsequently, the reaction mixture was heated to 80 °C for reaction and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 2.98 g of a white solid with a yield of 72.3%.

[0150] 11H NMR (500 MHz, Chloroform-d) δ 8.41 (t, J = 2.2 Hz, 1H), 8.08 (dd, J = 8.1, 2.3 Hz, 1H), 7.90–7.83 (m, 3H), 7.80 (dt, J = 9.9, 2.2 Hz, 2H), 7.73–7.66 (m, 1H), 7.60 (d, J = 2.2 Hz, 1H), 7.51–7.44 (m, 2H), 7.44–7.37 (m, 3H), 7.33–7.27 (m, 2H), 1.36 (s, 18H).

[0151] Synthesis of Compound 98g

[0152] 98f (2.8 g, 5.15 mmol, 1.0 e.q.), bis(pinacolato)diboron (1.82 g, 7.7 mmol, 1.5 e.q.), potassium acetate (1.5 g, 15.5 mmol, 3 e.q.), Pd(dppf) 2 Cl 2 (0.075 g, 0.103 mmol, 0.02 e.q.) and toluene (100 mL) were added to a flask. Stir at room temperature for 30 minutes, then heat to 80 °C and stir the reaction for 10 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The combined organic phases were dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residue was separated by silica gel column chromatography to obtain 2.68 g of a white powder with a yield of 82%.

[0153] 1 1H NMR (500 MHz, Chloroform-d) δ 8.42 (t, J = 2.2 Hz, 1H), 8.14 (dd, J = 8.1, 2.2 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.90–7.80 (m, 4H), 7.73–7.66 (m, 1H), 7.58 (d, J = 2.0 Hz, 1H), 7.51–7.41 (m, 2H), 7.44–7.37 (m, 2H), 7.33–7.27 (m, 2H), 1.35 (d, J = 7.1 Hz, 18H), 1.24 (s, 12H).

[0154] Synthesis of Compound 98h

[0155] Under protection, 98 g (2.5 g, 3.94 mmol, 1 e.q.), 2 g (1.3 g, 4.33 mmol, 1.1 e.q.), tetrakis(triphenylphosphine)palladium(0) (0.09 g, 0.08 mmol, 0.02 e.q.), potassium carbonate solution (2 M, 5.91 mL, 3 e.q.) and toluene (50 mL) were added to a three-necked flask. The flask was evacuated and filled with nitrogen, and this process was repeated three times. Subsequently, the reaction mixture was heated to 80 °C and stirred overnight. After cooling to room temperature, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated by silica gel column chromatography to obtain 1.21 g of a yellow solid with a yield of 48.9%.

[0156] 1 H NMR (500 MHz, Chloroform-d) δ 8.69 (s, 1H), 8.42 (t, J = 2.2 Hz, 1H), 8.13 (dd, J = 8.1, 2.4 Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.89–7.82 (m, 3H), 7.80 (t, J = 2.2 Hz, 1H), 7.72–7.66 (m, 1H), 7.63 (d, J = 2.0 Hz, 1H), 7.51–7.44 (m, 2H), 7.47–7.37 (m, 4H), 7.33–7.27 (m, 2H), 6.31 (d, J = 6.8 Hz, 1H), 1.35 (s, 27H).

[0157] Synthesis of Complex 98

[0158] A 250 mL single-necked flask was taken, and 72b (1.10 g, 1.75 mmol, 1 e.q.), potassium chloroplatinate (0.52 g, 2.1 mmol, 1.2 e.q.) and tetrabutylammonium bromide (50 mg) were dissolved in acetic acid (100 mL). Under nitrogen protection, the mixture was stirred at 135 °C for 24 hours. After cooling to room temperature, water was added to the reaction solution to precipitate a solid, and the crude product was obtained by filtration. Recrystallization from dichloromethane / n-hexane (1 / 1) gave 1.16 g of an orange-red powder with a yield of 81.3%.

[0159] 11H NMR (500 MHz, Chloroform-d) δ 8.19 (dd, J = 6.8, 1.4 Hz, 1H), 8.12–8.06 (m, 2H), 7.98 (dd, J = 8.2, 2.2 Hz, 1H), 7.92–7.86 (m, 2H), 7.57 (d, J = 8.2 Hz, 1H), 7.49–7.46 (m, 2H), 7.44–7.39 (m, 1H), 7.39–7.34 (m, 2H), 7.30 (d, J = 2.2 Hz, 1H), 7.26 (td, J = 7.0, 0.8 Hz, 1H), 7.06 (td, J = 7.1, 1.3 Hz, 1H), 6.46 (d, J = 6.0 Hz, 1H), 6.17 (d, J = 6.0 Hz, 1H), 1.36 (s, 27H).

[0160] 13 13C NMR (125 MHz, Common NMR Solvents) δ 155.88, 152.05, 151.70, 149.75, 147.24, 142.52, 139.89, 138.85, 138.13, 136.84, 136.54, 136.29, 130.61, 129.79, 129.05, 128.49, 128.37, 128.35, 127.75, 125.43, 124.26, 124.02, 123.78, 123.57, 123.18, 122.76, 118.88, 114.51, 107.80, 107.41, 38.62, 35.11, 34.93, 31.37, 31.27, 29.88.

[0161] ESI-HRMS (m / z): 822.318 (M+1).

[0162] Those skilled in the art should be aware that the above preparation methods are only several exemplary examples, and those skilled in the art can obtain other compound structures of the present invention by improving them.

[0163] Example 6:

[0164] An organic light-emitting diode is prepared using the luminescent material of the complex of the present invention, and the device structure is shown in Figure 1 .

[0165] First, the transparent conductive ITO glass substrate 10 (with the anode 20 on it) is successively washed with: a detergent solution and deionized water, ethanol, acetone, and deionized water, and then treated with oxygen plasma for 30 seconds.

[0166] Then, 10 nm thick HATCN is evaporated on the ITO as the hole injection layer 30.

[0167] Then, the compound HT was vapor-deposited to form a 40-nm-thick hole transport layer 40.

[0168] Then, a 20-nm-thick light-emitting layer 50 was vapor-deposited on the hole transport layer. The light-emitting layer was composed of a mixture of 20% platinum complex 2 and 80% CBP.

[0169] Then, 40 nm of AlQ was vapor-deposited on the light-emitting layer 3 as the electron transport layer 60.

[0170] Finally, 1 nm of LiF was vapor-deposited as the electron injection layer 70 and 100 nm of Al was deposited as the device cathode 80.

[0171] Example 7: Complex 10 was used to replace Complex 2, and an organic light-emitting diode was prepared by the method described in Example 6.

[0172] Example 8: Complex 20 was used to replace Complex 2, and an organic light-emitting diode was prepared by the method described in Example 6.

[0173] Example 9: Complex 44 was used to replace Complex 2, and an organic light-emitting diode was prepared by the method described in Example 6.

[0174] Example 10: Complex 98 was used to replace Complex 2, and an organic light-emitting diode was prepared by the method described in Example 6.

[0175] Comparative Example 1:

[0176] Complex Ref-1 (US10566566B2) was used to replace Complex 2, and an organic light-emitting diode was prepared by the method described in Example 6.

[0177] HATCN, HT, and AlQ in the device 3 , Ref-1, and the structural formula of RH are as follows:

[0178]

[0179] The device performances of the organic electroluminescent devices in Examples 6 - 10 and Comparative Example 1 at a current density of 10 mA / cm 2 are listed in Table 1:

[0180] Table 1

[0181]

[0182]

[0183] As can be seen from the data in Table 1, under the same conditions, the platinum complex material of the present invention can be used to prepare deep red organic light-emitting diodes, and has a lower driving voltage and a higher luminous efficiency. In addition, the device life of the organic light-emitting diode based on the complex of the present invention is significantly better than that of the complex material in the comparative example, can meet the requirements of the display industry for light-emitting materials, and has good industrialization prospects.

[0184] The above-mentioned various embodiments are only examples and are not used to limit the scope of the present invention. Without departing from the spirit of the present invention, various materials and structures in the present invention can be replaced by other materials and structures. It should be understood that those skilled in the art can make many modifications and changes according to the idea of the present invention without creative labor. Therefore, the technical solutions that can be obtained by those skilled in the art through analysis, reasoning or partial research on the basis of the prior art should all be within the protection scope defined by the claims.

Claims

1. The platinum complex of the NNCN tetradentate ligand is a compound having the structure of formula (I): Wherein ： A 1 , A 2 , P 1 The ring formed by the coordination bond with Pt is a six-membered ring; P 1 , P 2 The ring formed by the coordination bond with Pt is a five-membered ring; P 2 ,A 3 The ring formed by the coordination bond with Pt is a five-membered ring; wherein A 1 is selected from the group consisting of R 0 a substituted or unsubstituted N-containing heteroaryl having 4 to 20 carbon atoms; wherein the moiety bonded to A 2 , Pt is a five- or six-membered N-heterocycle; Wherein A 3 is selected from R 0 a substituted or unsubstituted heteroaryl containing one N or two N atoms and having 4 to 20 carbon atoms; wherein the part bonded to Pt is a five- or six-membered N heterocycle; Wherein A 2 is selected from R 0 a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, R 0 a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms; R 0 -R 5 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 aryl having 6-30 carbon atoms, or substituted or unsubstituted heteroaryl having 3-30 carbon atoms; said substitution is by halogen, cyano or C1-C4 alkyl; The heteroatom in the heteroaryl is one or more of N, S, and O.

2. The platinum complex according to claim 1, wherein R 0 -R 5 are each independently selected from: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, 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.

3. The platinum complex according to claim 2, wherein R 0 -R 5 are each independently selected from: hydrogen, deuterium, halogen, C1-C4 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.

4. The platinum complex according to claim 3, wherein R 0 -R 5 are 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 pyridyl, substituted or unsubstituted pyrazinyl, or substituted or unsubstituted pyrimidinyl.

5. The platinum complex according to claim 4, wherein A 2 is selected from R 0 a substituted or unsubstituted N-containing heteroaryl having 4 to 12 carbon atoms; wherein the bonding moiety with A 1 is a five- or six-membered N-heterocycle, and the position in A 2 bonded to A 1 is an N atom.

6. The platinum complex according to claim 1, wherein A 1 is selected from the following groups, wherein the dashed line represents the position of the bond linked to A 2 bond:

7. The platinum complex according to claim 1, wherein A 2 is selected from the following groups, wherein the dotted line represents the position of the bond to A 1 bond:

8. The platinum complex according to claim 1, wherein A 3 is selected from the following groups, where the dashed line represents the position of the bond to P 2 bond:

9. The platinum complex according to claim 1, wherein the general formula (I) is one of the following structures:

10. The precursor of the platinum complex according to claim 1, i.e., the ligand, has the following structural formula:

11. Use of any one of the platinum complexes of claims 1-9 in an organic optoelectronic device, wherein 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.

12. An organic light-emitting diode comprising a cathode, an anode, and an organic layer, wherein 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 any one of the platinum complexes of claims 1-9.

13. An organic light-emitting diode, wherein any one of the platinum complexes of claims 1-9 is a light-emitting material in the light-emitting layer or an electron transport material in the electron transport layer.

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