Highly efficient divalent platinum complexes phosphorescent oleds materials and applications thereof

Abstract

The present application relates to high-efficiency bivalent platinum complex phosphorescent OLED material and its application, platinum complex containing O N C N tetradentate ligand and its application in organic light emitting diode. The platinum complex is a compound with the structure of formula (I), which is applied in organic light emitting diode, has lower driving voltage and higher luminous efficiency, and can significantly improve the service life of the device, and has potential application in the field of organic electroluminescent devices. The present application also provides an organic electroluminescent device, which comprises a cathode, an anode and an organic layer, 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 of formula (I).

Description

TECHNICAL FIELD

[0001] The present application relates to the field of light-emitting materials, in particular to a platinum complex containing a high-efficiency tetradentate ligand and its application in organic light-emitting diodes. BACKGROUND

[0002] With the increasing demand for information, new intelligent terminal products are emerging, especially electronic products gradually develop towards intelligent, flexible and portable. Organic electroluminescence (OLEDs) is a new display technology, which has many advantages such as ultra-light and ultra-thin, low power consumption, self-luminous, wide temperature range, wide color gamut, wide viewing angle, fast response speed, and more easily to realize flexible display, and has become an important direction of current material science and industrial development.

[0003] Early developed fluorescent OLEDs can usually only utilize singlet state emission, and the triplet excitons generated in the device cannot be effectively utilized but return to the ground state through non-radiative way, which limits the popularization and use of OLEDs. In 1998, Professor B. Cheung of Hong Kong University first reported the electrophosphorescence phenomenon. In the same year, Thompson et al. prepared phosphorescent OLEDs using transition metal complexes as light-emitting materials. Phosphorescent OLEDs can efficiently utilize singlet and triplet excitons for light emission, and theoretically can achieve 100% internal quantum efficiency, which greatly promotes the commercialization process of OLEDs. The covalent metal-carbon bond of electrophosphorescent metal complexes increases the mixing of metal d orbitals and ligand orbitals, which can also improve the stability of the compound; and due to the strong heavy atom effect, the mixing of metal d orbitals and ligand orbitals can enhance the influence of the metal center on the excited state of the ligand itself, enhance the spin-orbit coupling effect, thereby improve the quantum yield of triplet state and promote efficient phosphorescent emission relaxation. After nearly two decades of research and development of electrophosphorescent OLEDs, it has also entered the stage of comprehensive improvement of efficiency and lifetime from the early stage of focusing only on efficiency breakthrough. How to maintain good multi-dimensional light-emitting device properties at high brightness is a new challenge for OLED research, and the problem of efficiency roll-off and shortening of service life after increasing brightness must be solved. The key to solving this problem lies in the continuous in-depth basic research on materials and device structure. The efficiency roll-off problem of OLED devices at high brightness mainly comes from exciton quenching in the light-emitting layer under high current density. Especially for phosphorescent dyes, the triplet exciton lifetime is long (~μs order), so it is more prone to triplet-triplet quenching, triplet-singlet and triplet-polaron quenching under high current density, resulting in efficiency roll-off at high brightness. Therefore, how to improve the exciton emission dynamics is the key to solving this problem. SUMMARY

[0004] In view of the above problems existing in the prior art, the present application provides a platinum complex luminescent material containing an OCN tetradentate ligand, which has good photoelectric performance and device lifetime when applied to an organic light-emitting diode.

[0005] The present application also provides an organic light-emitting diode based on the platinum complex.

[0006] The platinum complex containing the OCN tetradentate ligand is a compound having the structure of formula (I):

[0007]

[0008] wherein:

[0009] R 1 to R 24 are each independently selected from hydrogen, deuterium, halogen, amine group, carboxyl group, sulfanyl group, cyano group, sulfonyl group, phosphine group, substituted or unsubstituted alkyl group having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, substituted or unsubstituted alkenyl group having 2-20 carbon atoms, substituted or unsubstituted alkoxyl group having 1-20 carbon atoms, substituted or unsubstituted aryl group having 6-30 carbon atoms, substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, or connected or fused into a ring between any two adjacent substituents;

[0010] A1-A3 are selected from hydrogen, deuterium, halogen, amine group, carboxyl group, sulfanyl group, cyano group, sulfonyl group, phosphine group, substituted or unsubstituted alkyl group having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3-20 ring carbon atoms, substituted or unsubstituted alkenyl group having 2-20 carbon atoms, substituted or unsubstituted alkoxyl group having 1-20 carbon atoms, aryl group having 6-30 carbon atoms, substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, or connected or fused into a ring between any two adjacent substituents;

[0011] the heteroatoms in the heteroaryl group are one or more of N, S, O;

[0012] the substitution is substituted by halogen, deuterium, amine group, cyano group or C1-C4 alkyl.

[0013] Preferably, R 1 to R 24 are each independently selected from hydrogen, deuterium, halogen, amine group, sulfanyl 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 alkoxyl 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.

[0014] A1-A3 are selected from the group consisting of 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, aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms.

[0015] Preferably, R 1 to R 24 are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-6 carbon atoms;

[0016] one or more of A1-A3 are selected from the group consisting of halogen, cyano, substituted or unsubstituted alkyl having 1-6 carbon atoms, substituted or unsubstituted cycloalkyl having 3-12 ring carbon atoms, substituted or unsubstituted alkenyl having 2-12 carbon atoms, aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms, the remainder being hydrogen.

[0017] Further preferred, in general formula (I), R 1 to R 24 are each independently selected from the group consisting of hydrogen, deuterium, methyl, tert-butyl;

[0018] one or more of A1-A3 are selected from the group consisting of methyl, fluorine, cyano, tert-butyl, phenyl, cyano-phenyl, pyridyl; the remainder being hydrogen.

[0019] Preferred: wherein R 1 to R 24 R 1 -R 4 , R 10 -R 24 is hydrogen.

[0020] wherein R 5 -R 9 at least one of R 5 -R 9 is not hydrogen. 6 , R 8 is not hydrogen, R 5 , R 9 is hydrogen.

[0021] wherein R 5 -R 9 R 6 , R 8 is not hydrogen, R 5 , R 9 is hydrogen.

[0022] The following list examples of platinum metal complexes according to the present application, but is not limited to the structures listed:

[0023]

[0024]

[0025] The precursor of the above-mentioned metal complex, i.e. the ligand, has the following structural formula:

[0026]

[0027] R 1 to R 24 , A1-A3 are as described above.

[0028] The present application also provides a use of the above-mentioned platinum complex in an organic optoelectronic device, including but not limited to organic light-emitting diodes (OLEDs), organic thin-film transistors (OTFTs), organic photovoltaic devices (OPVs), light-emitting electrochemical cells (LCEs) and chemical sensors, preferably OLEDs.

[0029] An organic light-emitting diode (OLED) comprising the above-mentioned platinum complex, which is a light-emitting material in the light-emitting device.

[0030] The organic light-emitting diode in the present application comprises a cathode, an anode and an organic layer, the organic layer being 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, and these organic layers do not necessarily exist in each layer; at least one of the hole injection layer, the hole transport layer, the hole blocking layer, the light-emitting layer, the electron injection layer and the electron transport layer contains the platinum complex of formula (I).

[0031] Preferably, the layer containing the platinum complex of formula (I) is the light-emitting layer or the electron transport layer.

[0032] The total thickness of the organic layer of the device of the present application is 1-1000 nm, preferably 1-500 nm, and more preferably 5-300 nm.

[0033] The organic layer can be formed into a thin film by evaporation or solution method.

[0034] The series of novel platinum complex light-emitting materials disclosed in the present application show unexpected properties, significantly improving the light-emitting efficiency and device lifetime of the compounds, and having good thermal stability, meeting the requirements of OLED panels for light-emitting materials.

[0035] The compounds are applied in organic light-emitting diodes, have lower driving voltage and higher light-emitting efficiency, and can significantly improve the service life of the device, and have potential application in the field of organic electroluminescent devices. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 The structure of the organic light-emitting diode device of the present application is shown in the figure,

[0037] Where 10 represents the glass substrate, 20 represents the anode, 30 represents the hole injection layer, 40 represents the hole transport layer, 50 represents the light-emitting layer, 60 represents the electron transport layer, 70 represents the electron injection layer, and 80 represents the cathode. Detailed Implementation

[0038] This invention does not require specific methods for synthesizing the materials. The following examples are provided to illustrate the invention in more detail, but are not limited thereto. Unless otherwise specified, all raw materials used in the following synthesis are commercially available products.

[0039] Example 1:

[0040] Synthesis of complex 23b

[0041]

[0042] Synthesis of compound 23b:

[0043] Take a 250 mL single-necked flask, add 10.0 g (34.2 mmol) of 23a and 100 mL of diethyl ether at room temperature, replacing N2. Place the reaction apparatus in a cryogenic reactor at -78 °C and maintain the temperature for 30 minutes. After the temperature stabilizes, add 18 mL (37.6 mmol) of n-BuLi to the dropping funnel and add it slowly. After the addition is complete, maintain the temperature at -78 °C for one hour. At this time, add 3.85 g (37.6 mmol) of N-methoxy-N-methylacetamide to the dropping funnel and add it slowly. After the addition is complete, maintain the temperature for 30 minutes, slowly raise it to room temperature, and then transfer the reaction flask to room temperature and stir overnight. After the reaction is complete, extract three times with EA / H2O and separate by silica gel column chromatography (eluent: Hex / EA20 / 1) to obtain 7.0 g of yellow oil, with a yield of 77%.

[0044] 1 ¹H NMR (400MHz, CDCl₃) δ 7.89 (d, J = 10.7 Hz, 2H), 7.71 (s, 1H), 2.60 (s, 3H), 1.34 (s, 9H). Synthesis of compound 23c:

[0045] A 250 mL single-necked flask was filled with 23b (7.0 g, 27.4 mmol), elemental iodine (7.7 g, 30.2 mmol), and pyridine (86.8 g, 1.10 mol). The mixture was reacted at 130 °C for 16 h under nitrogen protection. After the reaction was complete, 200 mL of ethyl acetate was added to form a yellow precipitate. The precipitate was filtered, and the crude product was stirred three times with 250 mL of ethyl acetate at 80 °C. The mixture was then filtered and dried. 12.5 g of a flesh-colored powder was obtained, with a yield of 98%. 1H NMR (400MHz, DMSO) δ8.99(d,J=5.6Hz,2H),8.72(d,J=7.8Hz,1H),8.30–8.25(m,2H),8.03(s,1H),7.97(d,J=9.9Hz,2H),6.55(s,2H),1.32(s,9H).

[0046] Synthesis of compound 23d:

[0047] Two 250ml single-necked flasks were used. In the first flask, 23c (5.0g, 10.96mmol), intermediate a1 (3.2g, 9.13mmol), ammonium acetate (25g), and 50mL of acetic acid were added. In the second flask, 23c (7.8g, 16.95mmol), 23d (5.0g, 14.26mmol), ammonium acetate (39g), and 80mL of acetic acid were added. The mixture was reacted under nitrogen protection at 130℃ for 16 hours. After the reaction, most of the acetic acid solution and residual ammonium acetate solid were removed by multiple extractions with EA / H2O. Silica gel was then added, and the mixture was evaporated to dryness. The solution was packed into a column with pure HX. The column was eluted once with HX / EA40 / 1 and a second time with HX / THF 40 / 1. The remaining unpurified fraction was recrystallized multiple times with EA / CH3OH. The combined results yielded 7.75g of a pale yellow powder, with a yield of 58%.

[0048] 1 H NMR(400MHz, CDCl3)δ8.07(t,J=11.5Hz,4H),7.78(s,1H),7.62–7.58(m,2H),7.56(s,2H),7.45(t,J=7.8Hz,1H), 7.19(t,J=7.5Hz,1H),7.08(d,J=8.2Hz,1H),3.94(d,J=1.6Hz,3H),1.45(d,J=2.2Hz,18H),1.41(d,J=2.2Hz,9H).

[0049] Synthesis of compound 23e:

[0050] A 250 mL single-necked flask was filled with 23d (6.6 g, 10.68 mmol), B2Pin2 (5.81 g, 21.35 mmol), Pd(dppf)Cl2 (0.82 g, 1.07 mmol), KOAc (3.3 g, 32.34 mmol), and DMF (120 mL). The mixture was reacted under nitrogen protection at 85 °C for 16 h. After the reaction, most of the DMF was removed by rotary evaporation. The crude product was extracted with EA and water, dried, and then evaporated to dryness. The product was separated by column chromatography using EA / HX (1 / 10 to 1 / 4) as eluent. The impure fraction was recrystallized from EA / CH3OH to obtain 5.0 g of white powder, with a yield of 70%.

[0051] 1 H NMR (400MHz, CDCl3) δ8.29(d,J=12.5Hz,2H),8.07(dd,J=7.6,1.6Hz,1H),8.02(d,J=1.2Hz,1H),7.92(s,1H),7.85(s,1H),7.58-7 .51(m,3H),7.42(t,J=7.0Hz,1H),7.17(t,J=7.1Hz,1H),7.07(d,J=8.3Hz,1H),3.93(s,3H),1.43(d,J=5.1Hz,27H),1.38(s,12H).

[0052] Synthesis of compound 23f:

[0053] A 500 mL single-necked flask was filled with 23e (5.0 g, 8.2 mmol), a2 (2.08 g, 7.46 mmol), Pd(PPh3)4 (0.382 g, 0.37 mmol), Cs2CO3 (7.29 g, 22.38 mmol), and toluene / ethanol / water (100 / 100 / 25 mL). The mixture was reacted at 90 °C for 48 h under nitrogen protection. After the reaction was complete, most of the ethanol was removed by rotary evaporation. The crude product was extracted with EA and water, dried, and then evaporated to dryness. The product was separated by column chromatography using EA / HX 1 / 5 as eluent, and then recrystallized from EA / CH3OH to obtain 3.5 g of a white powder, with a yield of 64%.

[0054] 1H NMR (400MHz, CDCl3) δ8.88(d,J=5.1Hz,1H),8.51(d,J=11.8Hz,2H),8.21(s,2H),8.14(dd,J=15.0,7.3Hz,3H),8.01(d,J=5.3Hz,2H),7.88(s, 1H),7.58(d,J=4.9Hz,1H),7.53(s,4H),7.38(dd,J=14.1,6.5Hz,4H),7 .26(s,1H),7.13–7.02(m,2H),3.88(s,3H),1.47(s,9H),1.39(s,18H).

[0055] Synthesis of compound 23g:

[0056] A 250 mL single-necked flask was filled with 23f (3.5 g, 4.76 mmol), iodobenzene (2.86 g, 14.28 mmol), Cu (148.7 mg, 2.38 mmol), CuI (445.5 mg, 2.38 mmol), o-phenanthroline (843.5 mg, 4.76 mmol), Cs₂CO₃ (4.57 g, 14.28 mmol), and xylene (100 mL). Under nitrogen protection, the mixture was reacted at 160 °C for 24 h. A small amount of iodobenzene and catalyst were added, and the reaction continued for another 48 h. After the reaction was complete, the reaction solution was extracted with EA and water, dried, and evaporated to dryness. The solution was separated by column chromatography using EA / HX = 1 / 4 as the eluent, and then slurried with CH₃OH at 80 °C for 3 h to obtain 3.0 g of a white solid, with a yield of 79%.

[0057] 1 H NMR (400MHz, CDCl3) δ8.43(d,J=4.9Hz,1H),8.33(s,1H),8.28(dd,J=5.5,3.5 Hz,1H),8.22(d,J=6.6Hz,2H),8.08(dd,J=7.6,1.6Hz,1H),8.04(d,J=1.1Hz,1 H),7.99(s,1H),7.92(s,1H),7.57(s,3H),7.49-7.38(m,5H),7.35(t,J=7.3Hz ,1H),7.24(d,1H),7.20-7.01(m,8H),3.91(s,3H),1.50(s,9H),1.42(s,18H).

[0058] Synthesis of the complex after 23 hours:

[0059] Take a 250 mL single-necked flask, add 23 g (2.8 g, 3.36 mmol), pyridine hydrochloride (14 g), and o-dichlorobenzene (2.8 mL), and react under nitrogen protection at 200 °C for 8 h. After the reaction is complete, the reaction solution is extracted with DCM and water, dried, and evaporated to dryness. The solution is separated by column chromatography using HX / DCM / EA = 10 / 5 / 1 as the eluent, and then slurried with HX at 80 °C for 3 h to obtain 1.85 g of pale yellow solid, with a yield of 64%.

[0060] 1 H NMR(400MHz, CDCl3)δ8.40(d,J=4.9Hz,1H),8.29-8.24(m,1H),8.20(d,J=8.9Hz, 2H),8.09(s,1H),8.02(s,1H),7.94(d,J=9.4Hz,2H),7.87(s,1H),7.59(s,1H),7. 51(d,J=1.4Hz,2H),7.41(dd,J=10.4,6.8Hz,4H),7.33(t,J=7.6Hz,2H),7.27(s, 1H),7.07(dd,J=16.9,10.2Hz,6H),7.02-6.92(m,2H),1.49(s,9H),1.41(s,18H).

[0061] Synthesis of complex 23:

[0062] A 250 mL single-necked flask was filled with 1.7 g (2.10 mmol) of 23 h, 1.05 g (2.52 mmol) of K₂PtCl₄, 135 mg (0.42 mmol) of TBAB, and 150 mL of acetic acid. The mixture was reacted at 130 °C for 48 h under nitrogen protection. During the reaction, the solution gradually became turbid, and a yellow solid precipitated. After the reaction was complete, water was added to the solution to precipitate the solid. The precipitate was filtered, and the filtered solid was extracted once with DCM / water. The solid was then evaporated to dryness, packed into a column, and passed through a column with pure DCM. The first column product was evaporated to dryness again, and a second column was passed through the column using HX / DCM / EA = 2 / 1 / 0.3 as the eluent. The crude product was then recrystallized from DCM / HX to give 1.40 g of an orange-red solid, with a yield of 66.67%.

[0063] 1H NMR (400MHz, CDCl3) δ8.79(d,J=5.7Hz,1H),8.31(d,J=6.5Hz,1H),8.23(d,J=7.9Hz,2H),8.09(d,J=8.2Hz,1H),7.74(s,1H),7.63(d,J=9.1H z,2H),7.57(s,2H),7.52-7.29(m,9H),7.28(s,1H),7.19(s,2H),7.07 (t,J=7.8Hz,2H),6.92(s,1H),6.76(s,1H),1.43(s,17H),1.42(s,9H).

[0064] 13 C NMR (101MHz, CDCl3) δ169.02,168.78,166.57,153.46,152.55,152.20,151.64,150.91,149.78,148.65,143.53,141.69,141.26,141.19, 141.12,140.91,138.13,137.24,135.15,132.13,131.53,131.08,13 0.44,129.81,128.73,127.68,127.61,127.16,127.09,126.57,125.8 1,125.54,125.26,124.92,124.45,123.98,123.63,123.40,122.75,122.56,122.19,121.53,121.48,121.21,120.85,120.00,119.74,118.84,118.57,118.21,117.21,116.54,115.08,114.64,113.53,110.54,109.01,108.94,35.39,33.35,32.49,32.05,31.19,30.76,29.91.

[0065] ESI-MS (m / z): 1003.3 (M+1)

[0066] Those skilled in the art should understand that the above preparation method is merely an exemplary example, and they can obtain other compound structures of the present invention by improving it.

[0067] Example 2:

[0068]

[0069] Synthesis of compound 26b

[0070] 26a (10 g, 32.05 mmol) was dissolved in diethyl ether under nitrogen protection. The reaction mixture was stirred at -78 °C for 0.5 h, followed by the slow dropwise addition of n-BuLi (24.34 mL, 1.58 M, 38.46 mmol). After the addition was complete, the mixture was stirred at -78 °C for 0.5 h, followed by the slow dropwise addition of N-methoxy-N-methylacetamide (3.97 g, 38.46 mmol) and diethyl ether (200 mL). After the addition was complete, the mixture was stirred at -78 °C for 0.5 h, and then the temperature was raised to room temperature and stirred.

[0071] After the reaction was complete, the samples were combined and processed. A large amount of water was added until a precipitate formed. The solution was extracted three times with EA (100 ml), evaporated to dryness, and then separated by silica gel column chromatography (eluent: Hex:EA = 30:1). 18.4 g of a white solid was obtained, with a yield of 69.5%.

[0072] 1H NMR (400MHz, CDCl3) δ8.07(d,J=1.5Hz,1H),8.03(t,J=1.5Hz,1H),7.91(t,J=1.6Hz,1 H),7.60-7.55(m,2H),7.47(t,J=7.3Hz,2H),7.41(dd,J=8.4,6.1Hz,1H),2.63(s,3H).

[0073] Synthesis of compound 26c

[0074] Take a 1000 ml single-necked flask, add 26b (18 g, 65.42 mmol), p-toluenesulfonic acid-hydrate (24.89 g, 130.84 mmol), and acetonitrile (400 ml), and add NBS (11.64 g, 65.42 mmol) in portions, protected from light, and react at 60 °C for 2 h under nitrogen protection. After the reaction is complete, filter quickly through a silica gel funnel (eluent: EA), evaporate to dryness, and perform silica gel column chromatography (eluent: Hex:EA = 30:1 (V / V)) to obtain 18 g of yellow oily substance, with a yield of 77.7%.

[0075] 1 H NMR (400MHz, CDCl3) δ8.08(d,J=14.7Hz,2H),7.95(s,1H),7.58(s,1H),7.56(s,1H),7.48(t,J=7.4Hz,2H),7.42(t,J=7.2Hz,1H),4.50-4.42(m,2H).

[0076] Synthesis of compound 26d

[0077] Take a 1000 mL single-necked flask, add 18 g of 26 C (50.84 mmol, 1.0 eq) and pyridine (360 mL), and react under nitrogen protection at 130 °C for 6 h. After the reaction is complete, filter under vacuum, wash the solid twice with EA, and dry. 15 g of a pale yellow solid was obtained, with a yield of 68.11%.

[0078] 1 H NMR (400MHz, DMSO) δ9.02 (d, J = 5.7Hz, 2H), 8.74 (t, J = 7.8Hz, 1H), 8.29 (t, J = 7.5Hz, 4H), 8. 16(s,1H),7.81(d,J=7.3Hz,2H),7.53(t,J=7.4Hz,2H),7.46(t,J=7.3Hz,1H),6.63(s,2H).

[0079] Synthesis of compound 26e

[0080] A 500 mL single-necked flask was filled with 26d (10.0 g, 28.53 mmol), a1 (13.59 g, 31.38 mmol), NH4OAc (100 g, mixed with acetic acid in a 1:2 ratio), and acetic acid (200 mL). The mixture was reacted at 130 °C for 4 h under nitrogen protection. After the reaction was complete, water was added, and the mixture was extracted three times with DCM (50 mL). The organic phase was collected, evaporated to dryness, and separated by silica gel column chromatography (eluent: Hex:EA = 20:1). The eluent was then hot-pumped with methanol (80 °C). 15 g of a white solid was obtained, with a yield of 86.9%.

[0081] 1 H NMR (400MHz, CDCl3) δ8.26(d,J=8.5Hz,2H),8.08(d,J=1.1Hz,1H),8.04(dd,J=7.6,1.6Hz,1H),7.85-7.78(m,2H),7.66(d,J=7.2Hz,2H),7.55 (t,J=6.5Hz,3H),7.48(t,J=7.5Hz,2H),7.41(dd,J=13.4,7.2Hz,2H),7.17(t,J=7.3Hz,1H),7.07(d,J=8.2Hz,1H),3.92(s,3H),1.42(s,18H).

[0082] Synthesis of compound 26f

[0083] Take 250 ml of the three-way valve and add 26e (4.5 g, 7.45 mmol), pinacol diboronate (3.79 g, 14.91 mmol), Pd(OAc)2 (16.74 mg, 0.074 mmol), x-phos (356.89 mg, 0.74 mmol), KOAc (2.19 g, 22.36 mmol) and toluene (90 mL). Under nitrogen protection, react at 90 degrees Celsius for 16 h.

[0084] After the reaction was complete, the samples were combined and processed. The mixture was rapidly filtered through a silica gel funnel (eluent: EA). The solution was evaporated to dryness, and then separated by silica gel column chromatography (eluent: EA). The solution was then hot-beaten with Hex (80°C) to obtain 8.5 g of a white solid, with a yield of 87.6%.

[0085] 1 H NMR (400MHz, CDCl3) δ8.51(s,1H),8.46(s,1H),8.12(s,1H),8.09-8.01(m,2H),7.91(d,J=1.2Hz,1H),7.75(d,J=7.3Hz,2H),7.57-7.53 (m,3H),7.47(t,J=7.6Hz,2H),7.43-7.34(m,2H),7.16(t,J=7.4Hz,1H),7.06(d,J=8.2Hz,1H),3.92(s,3H),1.43(s,18H),1.39(s,12H).

[0086] Synthesis of compound 26g

[0087] Take a 250 mL single-necked flask and add 26f (2 g, 7.18 mmol, 1.0 eq), a2 (5.61 g, 8.61 mmol, 1.2 eq), Pd2(dba)3 (328.53 mg, 0.36 mmol, 0.05 eq), x-phos (342.06 mg, 0.72 mmol, 0.1 eq), K3PO4 3H2O (5.73 g, 21.53 mmol, 3.0 eq) and toluene / ethanol / water (40 mL / 10 mL / 10 mL). Under nitrogen protection, react at 80 °C for 4 h. After the reaction is complete, evaporate the solvent, extract three times with DCM (50 mL), collect the organic phase, and perform silica gel column chromatography (eluent: Hex:EA = 8:1), followed by hot homogenization with Hex (80 °C). 5.2 g of white solid was obtained, with a yield of 94.3%.

[0088] 1H NMR (400MHz, CDCl3) δ8.87(d,J=5.0Hz,1H),8.76(d,J=14.8Hz,2H),8.39(d,J=5.9H z,2H),8.22(s,1H),8.13(dd,J=14.4,7.7Hz,2H),8.06-7.99(m,2H),7.95(s,1H),7 .73(d,J=7.5Hz,2H),7.60-7.52(m,5H),7.45(t,J=7.6Hz,2H),7.41-7.34(m,5H),7 .27(dd,J=5.0,3.1Hz,1H),7.06(dd,J=15.4,7.9Hz,2H),3.89(s,3H),1.41(s,18H).

[0089] Synthesis of compound 26h

[0090] Take a 250ml single-necked flask and add 26g (5.0g, 6.51mmol, 1.0eq), iodobenzene (3.98g, 19.53mmol, 3.0eq), Cu (206.86mg, 3.26mmol, 0.5eq), CuI (619.96mg, 3.26mmol, 0.5eq), o-phenanthroline (1.17g, 6.51mmol, 1.0eq), Cs₂CO₃ (6.36g, 19.53mmol, 3.0eq), and xylene (100ml). Under nitrogen protection, react at 140℃ for 48h. Add iodobenzene (3.98g, 19.53mmol, 3.0eq), and react at 140℃ for 48h. Add iodobenzene again (3.98g, 19.53mmol, 3.0eq), and react at 140℃ for 24h. After the reaction was complete, the mixture was rapidly filtered through a silica gel funnel (EA), the solvent was evaporated, and silica gel column chromatography was performed (eluent: Hex:DCM:EA = 4:1:0.3). The mixture was then hot-particled with Hex (80°C). 5 g of a white solid was obtained, with a yield of 90.9%.

[0091] 1H NMR (400MHz, CDCl3) δ8.53 (s, 1H), 8.45-8.38 (m, 2H), 8.26 (t, J = 4.5Hz, 1H), 8. 20(d,J=7.9Hz,2H),8.09-8.03(m,2H),7.96(s,1H),7.78(d,J=7.1Hz,2H),7.55 (s,3H),7.50(dd,J=14.8,7.4Hz,3H),7.40(dd,J=13.9,5.8Hz,5H),7.33(t,J=7 .0Hz,1H),7.23(d,J=8.1Hz,1H),7.15-7.01(m,8H),3.89(s,3H),1.40(s,18H).

[0092] Synthesis of compound 26i

[0093] A 250 mL single-necked flask was filled with 5 g (5.92 mmol, 1.0 eq) of 26 h, 50 g of pyridine hydrochloride, and 5 mL of o-dichlorobenzene. The reaction was carried out under nitrogen protection at 200 °C for 5 h. After the reaction was complete, a large amount of water was added, and the mixture was extracted three times with DCM (30 mL). The organic phase was collected and separated by silica gel column chromatography (eluent: Hex:DCM:EA = 4:1:0.3), followed by hot homogenization with Hex (80 °C). 4.5 g of a yellow solid was obtained, with a yield of 91.5%.

[0094] 1 H NMR (400MHz, CDCl3) δ8.41 (d, J = 5.4Hz, 2H), 8.30-8.25 (m, 2H), 8.24-8.18 (m,2H),8.06(s,1H),7.99-7.92(m,2H),7.79(d,J=7.2Hz,2H),7.61(s,1H ),7.53(dd,J=13.4,4.7Hz,5H),7.46-7.38(m,4H),7.34(t,J=7.0Hz,2H), 7.28(d,J=8.1Hz,1H),7.18-7.05(m,6H),7.02-6.95(m,2H),1.43(s,18H).

[0095] Synthesis of Complex 26

[0096] 26i (1.5 g, 1.81 mmol, 1.0 eq), K₂PtCl₄ (900.13 mg, 2.17 mmol, 1.2 eq), TBAB (29.13 mg, 0.09 mmol, 0.05 eq), and acetic acid (150 ml) were reacted under nitrogen protection at 130 °C for 48 h. After the reaction, the samples were combined and processed. Water was added to precipitate the solid, which was filtered and washed twice with water. DCM was dissolved and the solid was separated by silica gel column chromatography (eluent: DCM). Further silica gel column chromatography (eluent: Hex:DCM:EA = 2:1:0.3) yielded 4.2 g of red solid. The crude product was recrystallized from DCM:Hex = 12 ml:12 ml to give 4 g of yellow solid, which was then recrystallized from DCM:MeOH = 12 ml:9 ml to give 3.7 g of yellow solid, with a yield of 66.7%.

[0097] 1 H NMR (400MHz, CDCl3) δ8.77 (d, J = 5.8 Hz, 1H), 8.33-8.20 (m, 3H), 8.07 (d, J = 8. 3Hz,1H),7.74(s,2H),7.62(s,1H),7.57(dd,J=10.0,4.6Hz,4H),7.46-7.40( m,8H),7.37(d,J=7.9Hz,2H),7.33-7.30(m,2H),7.15(d,J=4.0Hz,3H),7.07 (t,J=7.9Hz,2H),6.93(d,J=7.4Hz,1H),6.77(d,J=6.1Hz,1H),1.42(s,18H).

[0098] 13 C NMR (125MHz, Common NMR Solvents)δ166.22,152.06,151.60,146.44,144.39,143.26,140.34,140.20,140.07,140.07,139.59 ,139.54,139.32,138.96,138.92,137.72,137.14,131.64,130.52,130.17,130.07,129.41,129.16,1 28.64, 128.33, 128.06, 127.33, 126.91, 126.87, 125.92, 125.15, 124.75, 123.93, 123.60, 123.50, 123.47, 123.44, 122.86, 122.63, 122.30, 121.69, 121.59, 120.81, 120.47, 113.76, 112.54, 34.96, 31.29.

[0099] ESI-MS (m / z): 1023.3 (M+1)

[0100] Example 3:

[0101]

[0102] Synthesis of compound 41b:

[0103] Take a 250 mL single-necked flask, add 10.0 g (29.6 mmol) of 41a and 100 mL of diethyl ether at room temperature, replacing N2. Place the reaction apparatus in a cryogenic reactor at -78 °C and maintain the temperature for 30 minutes. After the temperature stabilizes, add n-BuLi (20.8 mL, 32.6 mmol) slowly dropwise to a dropping funnel. After the addition is complete, maintain the temperature at -78 °C for one hour. At this time, add N-methoxy-N-methylacetamide (3.36 g, 32.6 mmol) slowly dropwise to a dropping funnel. After the addition is complete, maintain the temperature for 30 minutes, slowly raise it to room temperature, and then transfer the reaction flask to room temperature and stir overnight. After the reaction is complete, extract three times with EA / H2O, and separate by silica gel column chromatography (eluent: Hex / EA 20 / 1) to obtain 6.4 g of yellow oil, with a yield of 72.3%.

[0104] 1 H NMR (400MHz, CDCl3) δ8.38(d,J=1.9Hz,1H),7.98(s,1H),7.83(dd,J=8.3,1.9Hz,1H),7.69(d,J=8.3 Hz,1H),7.66(dt,J=6.6,1.7Hz,1H),7.62(dt,J=6.4,1.4Hz,1H),7.58(t,J=6.5Hz,1H),2.60(s,3H).

[0105] Synthesis of compound 41c:

[0106] A 250 mL single-necked flask was filled with 41b (6.0 g, 20.0 mmol), elemental iodine (5.6 g, 22.0 mmol), and pyridine (63.1 g, 0.80 mol). The mixture was reacted at 130 °C for 16 h under nitrogen protection. After the reaction was complete, 200 mL of ethyl acetate was added to form a yellow precipitate. The precipitate was filtered, and the crude product was stirred three times with 250 mL of ethyl acetate at 80 °C. The mixture was then filtered and dried. 9.8 g of a pink powder was obtained, with a yield of 97%. 1H NMR (400MHz, DMSO) δ9.13 (dt, J=5.4, 1.3Hz, 2H), 8.65 (tt, J=7.9, 1.3Hz, 1H), 8.27-8.20 (m, 2H), 8.04-7. 97(m,3H),7.76(d,J=8.3Hz,1H),7.64(ddt,J=16.1,6.4,1.4Hz,2H),7.58(t,J=6.5Hz,1H),6.66(s,2H).

[0107] Synthesis of compound 41d:

[0108] Two 250ml single-necked flasks were used. In the first flask, 9.0g of 41c (17.81mmol), intermediate a1 (5.20g, 14.85mmol), 45g of ammonium acetate, and 90mL of acetic acid were added. The mixture was reacted under nitrogen protection at 130℃ for 20h. After the reaction, most of the acetic acid solution and residual ammonium acetate solid were removed by extraction with EA / H2O multiple times. Silica gel was then added, and the mixture was evaporated to dryness. The solution was packed into a column with pure HX. The column was run once with HX / EA40 / 1 as the eluent and a second time with HX / THF 40 / 1 as the eluent. The remaining unpurified fraction was recrystallized multiple times with EA / CH3OH. The two reactions were combined to obtain 7.06g of pale yellow powder, with a yield of 63%.

[0109] 1 H NMR (400MHz, CDCl3) δ8.11(dd,J=2.0,1.4Hz,2H),7.92(dd,J=8.4,1.6Hz,2H),7.81( dd,J=6.2,1.5Hz,1H),7.75(d,J=8.4Hz,1H),7.71-7.66(m,2H),7.55(td,J=7.4,1.6 Hz,1H),7.52-7.46(m,2H),7.43(d,J=2.2Hz,2H),7.38(td,J=7.6,1.1Hz,2H),7.15( ddd,J=8.6,7.5,1.1Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).

[0110] Synthesis of compound 41e:

[0111] A 250 mL single-necked flask was filled with 41d (6.5 g, 10.32 mmol), B2Pin2 (5.24 g, 20.64 mmol), Pd(dppf)Cl2 (0.79 g, 1.03 mmol), KOAc (3.0 g, 30.96 mmol), and DMF (120 mL). The mixture was reacted under nitrogen protection at 85 °C for 16 h. After the reaction, most of the DMF was removed by rotary evaporation. The crude product was extracted with EA and water, dried, and then evaporated to dryness. The product was separated by column chromatography using EA / HX (1 / 10 to 1 / 4) as eluent. The impure fraction was recrystallized from EA / CH3OH to obtain 5.1 g of a white powder, with a yield of 73%.

[0112] 1 H NMR(400MHz, CDCl3)δ8.42(d,J=1.9Hz,1H),8.11-8.05(m,2H),7.92(dd,J=8.4,1.6 Hz,2H),7.81(dd,J=6.2,1.5Hz,1H),7.76-7.69(m,2H),7.55(td,J=7.4,1.6Hz,1H), 7.49(s,2H),7.43(d,J=2.2Hz,2H),7.38(td,J=7.6,1.1Hz,1H),7.15(ddd,J=8.6,7. 5,1.1Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H),1.24(s,12H).

[0113] Synthesis of compound 41f:

[0114] A 500 mL single-necked flask was filled with 41e (5.0 g, 7.3 mmol), a2 (1.85 g, 6.64 mmol), Pd(PPh3)4 (0.382 g, 0.33 mmol), Cs2CO3 (6.4 g, 19.92 mmol), and toluene / ethanol / water (100 / 100 / 25 mL). The mixture was reacted under nitrogen protection at 90 °C for 48 h. After the reaction was complete, most of the ethanol was removed by rotary evaporation. The crude product was extracted with EA and water, dried, and then evaporated to dryness. The product was separated by column chromatography using EA / HX 1 / 5 as eluent, and then recrystallized from EA / CH3OH to obtain 3.8 g of a white powder, with a yield of 67%.

[0115] 1H NMR (400MHz, CDCl3) δ9.38(d,J=1.7Hz,1H),8.80(d,J=4.4Hz,1H),8.26(d,J=2.2Hz,1H),8.1 7-8.11(m,3H),7.95-7.85(m,4H),7.85-7.79(m,2H),7.70(dd,J=7.5,1.4Hz,1H),7.55(td,J= 7.4,1.6Hz,1H),7.52-7.44(m,3H),7.43(d,J=2.2Hz,2H),7.41-7.31(m,3H),7.27-7.20(m,1 H),7.15(ddd,J=8.6,7.5,1.1Hz,1H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).

[0116] Synthesis of compound 41g:

[0117] A 250 mL single-necked flask was filled with 41f (3.5 g, 4.4 mmol), iodobenzene (2.69 g, 13.2 mmol), Cu (144.1 mg, 2.2 mmol), CuI (418.9 mg, 2.2 mmol), o-phenanthroline (792.9 mg, 4.4 mmol), Cs₂CO₃ (4.30 g, 13.2 mmol), and xylene (100 mL). Under nitrogen protection, the mixture was reacted at 160 °C for 24 h. A small amount of iodobenzene and catalyst were added, and the reaction continued for another 48 h. After the reaction was complete, the reaction solution was extracted with EA and water, dried, and evaporated to dryness. The solution was separated by column chromatography using EA / HX = 1 / 4 as the eluent, and then slurried with CH₃OH at 80 °C for 3 h to obtain 2.75 g of a white solid, with a yield of 72%.

[0118] 1 H NMR (400MHz, CDCl3) δ9.38(d,J=1.7Hz,1H),8.76(d,J=4.5Hz,1H),8.28(d,J=2.2Hz,1H),8.17 -8.11(m,2H),8.09(dt,J=6.9,0.7Hz,1H),7.95-7.85(m,4H),7.81(dd,J=6.2,1.5Hz,1H),7.6 8(ddd,J=14.5,6.8,1.4Hz,2H),7.62(dd,J=7.0,0.7Hz,1H),7.59-7.47(m,6H),7.45-7.26(m, 9H), 7.15 (ddd, J=8.6, 7.5, 1.1Hz, 1H), 6.90 (dd, J=7.7, 1.2Hz, 1H), 3.90 (s, 3H), 1.35 (s, 18H).

[0119] Synthesis of complex 41h:

[0120] Take a 250 mL single-necked flask, add 41 g (3 g, 3.45 mmol), pyridine hydrochloride (15 g), and o-dichlorobenzene (3 mL), and react under nitrogen protection at 200 °C for 8 h. After the reaction is complete, the reaction solution is extracted with DCM and water, dried, and evaporated to dryness. The solution is separated by column chromatography using HX / DCM / EA = 10 / 5 / 1 as the eluent, and then slurried with HX at 80 °C for 3 h to obtain 1.77 g of pale yellow solid, with a yield of 60%.

[0121] 1 H NMR (400MHz, CDCl3) δ9.38(d,J=1.7Hz,1H),8.76(d,J=4.5Hz,1H),8.28(d,J=2.2Hz,1H),8.14 (dd,J=7.4,1.8Hz,2H),8.12-8.06(m,1H),8.00(dd,J=8.7,1.2Hz,1H),7.94-7.85(m,3H),7.8 1(dd,J=6.2,1.5Hz,1H),7.68(ddd,J=14.5,6.8,1.4Hz,2H),7.62(dd,J=7.0,0.7Hz,1H),7.58 -7.47(m,6H),7.46-7.28(m,8H),7.25(td,J=8.0,1.3Hz,1H),7.02-6.94(m,2H),1.35(s,18H).

[0122] Synthesis of complex 41:

[0123] A 250 mL single-necked flask was filled with 1.5 g (1.75 mmol) of 41 h, 0.79 g (2.1 mmol) of K₂PtCl₄, 112.8 mg (0.35 mmol) of TBAB, and 120 mL of acetic acid. The mixture was reacted at 130 °C for 48 h under nitrogen protection. During the reaction, the solution gradually became turbid, and a yellow solid precipitated. After the reaction was complete, water was added to the solution to precipitate the solid. The precipitate was filtered, and the filtered solid was extracted once with DCM / water. The solid was then evaporated to dryness, packed into a column, and passed through a column with pure DCM. The first column product was evaporated to dryness again, and a second column was passed through the column using HX / DCM / EA = 2 / 1 / 0.3 as the eluent. The crude product was then recrystallized from DCM / HX to give 1.50 g of an orange-red solid, with a yield of 81.79%.

[0124] 1H NMR (400MHz, CDCl3) δ9.10(d,J=8.9Hz,1H),8.28(d,J=2.1Hz,1H),8.18-8.12(m,1H),8.09(dt,J=6.6,0.8H z,1H),8.04(d,J=8.4Hz,1H),7.94(dd,J=8.3,1.2Hz,1H),7.92-7.86(m,2H),7.75(dd,J=9.4,2.3Hz,2H),7. 70(d,J=2.2Hz,1H),7.67(dd,J=6.2,1.7Hz,1H),7.62(dd,J=7.5,1.5Hz,1H),7.60-7.47(m,7H),7.45-7.27( m,8H),7.18(dd,J=7.5,1.3Hz,1H),7.09(ddd,J=8.4,7.5,1.3Hz,1H),6.90(d,J=2.9Hz,2H),1.35(s,18H)..

[0125] 13 C NMR (101MHz, CDCl3) δ166.24,152.13,151.60,148.10,144.64,144.12,140.90,140.24,139.59,139.32,138.9 3,138.92,138.22,137.16,136.19,134.35,133.21,132.84,131.64,131.57,131.49,130.53,130.05,128.67, 128.33,128.06,127.52,127.50,126.91,126.87,125.77,125.15,124.75,123.93,123.50,123.47,123.44,122.86,122.83,122.63,122.39,121.69,121.59,120.81,120.47,117.66,113.76,112.54,109.43,34.96,31.29.

[0126] ESI-MS (m / z): 1048.3 (M+1)

[0127] Example 4:

[0128]

[0129]

[0130] Synthesis of compound 52b:

[0131] Take a 250 mL single-necked flask, add 10.0 g (24.8 mmol) of 52a and 100 mL of diethyl ether at room temperature, replacing N2. Place the reaction apparatus in a cryogenic reactor at -78 °C and maintain the temperature for 30 minutes. After the temperature stabilizes, add n-BuLi (17.4 mL, 27.28 mmol) slowly dropwise to a dropping funnel. After the addition is complete, maintain the temperature at -78 °C for one hour. At this time, add N-methoxy-N-methylacetamide (2.81 g, 27.28 mmol) slowly dropwise to a dropping funnel. After the addition is complete, maintain the temperature for 30 minutes, slowly raise it to room temperature, and then transfer the reaction flask to room temperature and stir overnight. After the reaction is complete, extract three times with EA / H2O, and separate by silica gel column chromatography (eluent: Hex / EA 20 / 1) to obtain 7.2 g of yellow oil, with a yield of 79.7%.

[0132] 1 ¹H NMR (400MHz, CDCl₃) δ 7.84 (t, J = 2.1Hz, 1H), 7.59 (t, J = 2.2Hz, 1H), 7.44 (t, J = 2.2Hz, 1H), 7.28 (tt, J = 7.7, 1.5Hz, 4H), 7.14–7.08 (m, 4H), 7.04 (tt, J = 7.6, 1.4Hz, 2H), 2.61 (s, 3H). Synthesis of compound 52c:

[0133] A 250 mL single-necked flask was filled with 52b (7.0 g, 19.1 mmol), elemental iodine (5.3 g, 21.0 mmol), and pyridine (60.4 g, 0.76 mol). The mixture was reacted at 130 °C for 16 h under nitrogen protection. After the reaction was complete, 200 mL of ethyl acetate was added to form a yellow precipitate. The precipitate was filtered, and the crude product was stirred three times with 250 mL of ethyl acetate at 80 °C. The mixture was then filtered and dried. 10.5 g of a pink powder was obtained, with a yield of 97%.

[0134] 1 H NMR (400MHz, DMSO) δ9.13 (dd, J=6.6, 1.3Hz, 2H), 8.65 (tt, J=7.9, 1.3Hz, 1H), 8.26-8.20 (m, 2H), 7.93 (t, J=2.2Hz, 1H), 7.67 (t ,J=2.2Hz,1H),7.44(t,J=2.2Hz,1H),7.28(tt,J=7.6,1.5Hz,4H),7.14-7.08(m,4H),7.04(tt,J=7.7,1.4Hz,2H),6.70(s,2H).

[0135] Synthesis of compound 52d:

[0136] Two 250ml single-necked flasks were used. In the first flask, 10.0g (17.5mmol) of 52C, 5.12g (14.6mmol) of intermediate a1, 50g of ammonium acetate, and 90mL of acetic acid were added. The mixture was reacted under nitrogen protection at 130℃ for 20h. After the reaction, most of the acetic acid solution and residual ammonium acetate solid were removed by extraction with EA / H2O multiple times. Silica gel was then added, and the mixture was evaporated to dryness. The solution was packed into a column with pure HX. The column was run once with HX / EA 40 / 1 as the eluent and a second time with HX / THF 40 / 1 as the eluent. The remaining unpurified fraction was recrystallized multiple times with EA / CH3OH. The two reactions were combined to obtain 8.03g of pale yellow powder, with a yield of 66%.

[0137] 1 H NMR (400MHz, CDCl3) δ8.09(d,J=2.2Hz,1H),7.99(t,J=2.1Hz,1H),7.95-7.89(m,2H),7.50(td,J=2.2,0.7Hz,1H),7.44-7.35(m,4H) ,7.28(tt,J=7.6,1.5Hz,4H),7.18-7.08(m,5H),7.04(tt,J=7.7,1.4Hz,2H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).

[0138] Synthesis of compound 52e:

[0139] A 250 mL single-necked flask was filled with 52d (7 g, 10.06 mmol), B2Pin2 (5.11 g, 20.12 mmol), Pd(dppf)Cl2 (0.73 g, 1.0 mmol), KOAc (2.98 g, 30.36 mmol), and DMF (120 mL). The mixture was reacted under nitrogen protection at 85 °C for 16 h. After the reaction, most of the DMF was removed by rotary evaporation. The crude product was extracted with EA and water, dried, and then evaporated to dryness. The product was separated by column chromatography using EA / HX (1 / 10 to 1 / 4) as eluent. The impure fraction was recrystallized from EA / CH3OH to obtain 5.3 g of a white powder, with a yield of 71%.

[0140] 1H NMR (400MHz, CDCl3) δ8.08(d,J=2.2Hz,1H),7.94-7.89(m,2H),7.81(t,J=2.2Hz,1H),7.52-7.47(m,2H),7.44-7.35(m,3H),7.33- 7.25(m,5H),7.18-7.08(m,5H),7.04(tt,J=7.7,1.4Hz,2H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H),1.24(s,12H).

[0141] Synthesis of compound 52f:

[0142] A 500 mL single-necked flask was filled with 52e (5.0 g, 6.7 mmol), a2 (1.7 g, 6.1 mmol), Pd(PPh3)4 (0.382 g, 0.33 mmol), Cs2CO3 (6.1 g, 18.76 mmol), and toluene / ethanol / water (100 / 100 / 25 mL). The mixture was reacted under nitrogen protection at 90 °C for 48 h. After the reaction was complete, most of the ethanol was removed by rotary evaporation. The crude product was extracted with EA and water, dried, and then evaporated to dryness. The product was separated by column chromatography using EA / HX 1 / 5 as eluent, and then recrystallized from EA / CH3OH to obtain 4.2 g of a white powder, with a yield of 73%.

[0143] 1 H NMR (400MHz, CDCl3) δ8.79(d,J=4.5Hz,1H),8.24(d,J=2.2Hz,1H),8.21(t,J=2.2Hz,1H),8.14(ddd,J=7.7,4.1,1.0H z,2H),8.10(d,J=2.2Hz,1H),7.97-7.90(m,2H),7.82(dd,J=7.5,0.8Hz,1H),7.56(dt,J=4.7,2.2Hz,2H),7.51-7.45( m,3H),7.42(d,J=2.1Hz,2H),7.40-7.32(m,3H),7.28(dd,J=7.8,7.0Hz,4H),7.26-7.20(m,1H),7.15(ddd,J=8.6,7. 5,1.1Hz,1H),7.12-7.08(m,4H),7.04(tt,J=7.7,1.4Hz,2H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).

[0144] Synthesis of compound 52g:

[0145] A 250 mL single-necked flask was filled with 52f (4 g, 4.3 mmol), iodobenzene (2.63 g, 12.9 mmol), Cu (136.6 mg, 2.15 mmol), CuI (409.5 mg, 2.15 mmol), o-phenanthroline (774.9 mg, 4.3 mmol), Cs₂CO₃ (4.20 g, 12.9 mmol), and xylene (100 mL). Under nitrogen protection, the mixture was reacted at 160 °C for 24 h. A small amount of iodobenzene and catalyst were added, and the reaction continued for another 48 h. After the reaction was complete, the reaction solution was extracted with EA and water, dried, and evaporated to dryness. The solution was separated by column chromatography using EA / HX = 1 / 4 as the eluent, and then slurried with CH₃OH at 80 °C for 3 h to obtain 2.9 g of a white solid, with a yield of 72%.

[0146] 1 H NMR (400MHz, CDCl3) δ8.75(d,J=4.4Hz,1H),8.24(d,J=2.2Hz,1H),8.21(t,J=2.2Hz,1H),8.17-8.13(m,1H), 8.11-8.06(m,2H),7.95-7.89(m,2H),7.67(dd,J=6.2,1.7Hz,1H),7.62(dd,J=7.0,0.7Hz,1H),7.56(dt,J=4. 7,2.2Hz,2H),7.54-7.47(m,4H),7.45-7.41(m,4H),7.41-7.26(m,9H),7.15(ddd,J=8.6,7.5,1.1Hz,1H),7.1 1(dd,J=7.1,1.3Hz,4H),7.04(tt,J=7.7,1.4Hz,2H),6.90(dd,J=7.7,1.2Hz,1H),3.90(s,3H),1.35(s,18H).

[0147] Synthesis of the complex after 52 hours:

[0148] Take a 250 mL single-necked flask, add 52 g (2.5 g, 2.67 mmol), pyridine hydrochloride (12.5 g), and o-dichlorobenzene (2.5 mL), and react under nitrogen protection at 200 °C for 8 h. After the reaction is complete, the reaction solution is extracted with DCM and water, dried, and evaporated to dryness. The solution is separated by column chromatography using HX / DCM / EA = 10 / 5 / 1 as the eluent, and then slurried with HX at 80 °C for 3 h to obtain 2 g of pale yellow solid, with a yield of 81.3%.

[0149] 1H NMR (400MHz, CDCl3) δ8.75(d,J=4.4Hz,1H),8.24(d,J=2.2Hz,1H),8.21(t,J=2.2Hz,1H),8. 18-8.13(m,1H),8.11-8.06(m,2H),7.99(dd,J=8.8,1.3Hz,1H),7.85(d,J=2.2Hz,1H),7.67 (dd, J = 6.2, 1.7 Hz, 1H), 7.62 (dd, J = 7.0, 0.7 Hz, 1H), 7.56 (dt, J = 4.7, 2.2 Hz, 2H), 7.54-7.45 (m, 4H), 7.45-7.18 (m, 13H), 7.14-7.08 (m, 4H), 7.08-6.94 (m, 4H), 1.35 (s, 18H). Synthesis of complex 52:

[0150] A 250 mL single-necked flask was filled with 1.5 g (1.62 mmol) of 52 h, 0.71 g (1.9 mmol) of K₂PtCl₄, 104.4 mg (0.324 mmol) of TBAB, and 120 mL of acetic acid. The mixture was reacted at 130 °C for 48 h under nitrogen protection. During the reaction, the solution gradually became turbid, and a yellow solid precipitated. After the reaction was complete, water was added to the solution to precipitate the solid. The precipitate was filtered, and the filtered solid was extracted once with DCM / water. The solid was then evaporated to dryness, packed into a column, and passed through a column with pure DCM. The first column product was evaporated to dryness again, and a second column was passed through the column using HX / DCM / EA = 2 / 1 / 0.3 as the eluent. The crude product was then recrystallized from DCM / HX to give 1.50 g of an orange-red solid, with a yield of 83.1%.

[0151] 1 H NMR(400MHz, CDCl3)δ9.05(d,J=8.9Hz,1H),8.23(d,J=2.2Hz,1H),8.16-8.12( m,1H),8.11-8.06(m,2H),7.94(dd,J=8.2,1.2Hz,1H),7.75(dd,J=9.3,2.3Hz, 2H),7.70-7.64(m,3H),7.56-7.47(m,5H),7.45-7.25(m,12H),7.20-7.14(m,2 H),7.13-7.07(m,5H),7.04(tt,J=7.7,1.4Hz,2H),6.91(s,1H),1.35(s,18H).

[0152] 13C NMR (101MHz, CDCl3) δ166.22,152.05,151.60,147.81,147.38,146.01,144.39,142.70,140.34,139.59,1 39.32,138.96,138.92,137.14,134.45,134.12,131.74,131.64,130.52,130.07,129.32,128.33,128.06, 126.91,126.87,125.95,125.20,125.16,125.15,124.75,124.31,123.93,123.52,123.50,123.47,123.44,123.29,122.86,122.63,122.10,121.90,121.69,121.59,120.81,120.47,113.76,112.54,34.96,31.29.

[0153] ESI-MS (m / z): 1114.4 (M+1)

[0154] Example 5:

[0155] Under a nitrogen atmosphere, approximately 5.0 mg of thoroughly dried platinum complex 23.26.41.52 samples were weighed. The heating scan rate was set to 10 °C / min, and the scan range was 25-800 °C. The thermal decomposition temperatures were measured to be 418.5, 472.6, 478.9, and 491 °C (temperatures corresponding to 0.5% thermal weight loss), indicating that this type of complex has excellent thermal stability.

[0156] Example 6:

[0157] Organic light-emitting diodes were fabricated using the complex luminescent materials of the present invention. The device structure is shown in [see figure]. Figure 1 .

[0158] First, the transparent conductive ITO glass substrate 10 (with an anode 20 on it) is washed sequentially with detergent solution and deionized water, ethanol, acetone, and deionized water, and then treated with oxygen plasma for 30 seconds.

[0159] Then, a 10 nm thick HATCN layer was deposited on ITO as a hole injection layer 30.

[0160] Then, the compound HT is evaporated to form a 40 nm thick hole transport layer 40.

[0161] Then, a 20 nm thick light-emitting layer 50 is deposited on the hole transport layer. The light-emitting layer is composed of a mixture of platinum complex 23 (20%) and CBP (80%).

[0162] Then, a 40 nm thick AlQ3 layer is deposited on the light-emitting layer as an electron transport layer 60.

[0163] Finally, 1 nm LiF was deposited as the electron injection layer 70 and 100 nm Al was deposited as the device cathode 80.

[0164] Example 8: Organic light-emitting diodes were prepared by replacing complex 23 with complex 26 using the method described in Example 6.

[0165] Example 9: Organic light-emitting diodes were prepared by replacing complex 23 with complex 41 using the method described in Example 6.

[0166] Example 10: Organic light-emitting diodes were prepared by replacing complex 23 with complex 52 using the method described in Example 6.

[0167] Comparative Example 1:

[0168] Organic light-emitting diodes were prepared by replacing complex 9 with complex Ref-1 (CN110872325A) using the method described in Example 6.

[0169] Comparative Example 2:

[0170] Organic light-emitting diodes were prepared by replacing complex 9 with complex Ref-2 (Chem. Sci., 2014, 5, 4819) using the method described in Example 6.

[0171] Comparative Example 3:

[0172] Organic light-emitting diodes were prepared by replacing complex 9 with complex Ref-3 (CN110872325A) using the method described in Example 6.

[0173] Comparative Example 4:

[0174] Organic light-emitting diodes were prepared by replacing complex 9 with complex Ref-4 (CN110872325A) using the method described in Example 6.

[0175] The structural formulas of HATCN, HT, AlQ3, Ref-1, Ref-2, Ref-3, Ref-4 and CBP in the device are as follows:

[0176]

[0177]

[0178] The organic electroluminescent devices in Examples 6, 8-10, Comparative Examples 1, 2, 3, and 4 at 20 mA / cm2 The device performance at current density is listed in Table 1:

[0179] Table 1

[0180]

[0181] As shown in Table 1, under the same conditions, the platinum complex material of this invention, when applied to organic light-emitting diodes (OLEDs), exhibits a lower driving voltage and higher luminous efficiency. Furthermore, the device lifetime of OLEDs based on the complexes of this invention is significantly better than that of the complexes in the comparative examples, meeting the requirements of the display industry for luminescent materials and demonstrating promising industrialization prospects.

[0182] The above-described embodiments are merely examples and are not intended to limit the scope of the invention. Without departing from the spirit of the invention, various materials and structures in this invention can be replaced with other materials and structures. It should be understood that those skilled in the art can make many modifications and variations based on the concept of the invention without creative effort. Therefore, technical solutions that can be obtained by those skilled in the art through analysis, reasoning, or partial research based on the prior art should all be within the scope of protection defined by the claims.

Claims

1. Platinum complexes containing ONCN tetradentate ligands are compounds with the structure of formula (I): R 1 To R 24 Each is independently selected from: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl groups having 1-20 carbon atoms, or substituted or unsubstituted alkoxy groups having 1-20 carbon atoms; One or more of A1-A3 are selected from halogen, cyano, substituted or unsubstituted alkyl with 1-6 carbon atoms, or substituted or unsubstituted aryl with 6-30 carbon atoms, and the remainder is hydrogen; The substitution is achieved by halogen, deuterium, cyano, or C1-C4 alkyl groups.

2. The platinum complex according to claim 1, wherein R 1 To R 24 Each is independently selected from: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl groups having 1-6 carbon atoms, or substituted or unsubstituted alkoxy groups having 1-6 carbon atoms.

3. The platinum complex according to claim 2, wherein R 1 To R 24 Each is independently selected from: hydrogen, deuterium, halogen, or substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.

4. The platinum complex according to claim 2, wherein, In general formula (I), R 1 To R 24 Each is independently selected from: hydrogen, deuterium, methyl, or tert-butyl; One or more of A1-A3 are selected from methyl, fluorine, cyano, tert-butyl, phenyl, or cyanophenyl; the rest are hydrogen.

5. The platinum complex according to any one of claims 1-4, wherein R 1 To R 24 Chinese R 1 -R 4 R 10 -R 24 It is hydrogen.

6. The platinum complex according to claim 5, wherein R 5 -R 9 At least one of them is not hydrogen.

7. The platinum complex according to claim 6, wherein R 5 -R 9 Chinese R 6 R 8 Not hydrogen, R 5 R 9 It is hydrogen.

8. A platinum complex containing an ONCN tetradentate ligand is one of the following compounds:

9. A precursor, i.e., a ligand, of a platinum complex has the following structural formula: R 1 To R 24 A1-A3 are as described in any one of claims 1-7.

10. The use of the platinum complex according to any one of claims 1-8 in organic light-emitting diodes, organic thin-film transistors, organic photovoltaic devices, luminescent electrochemical cells, or chemical sensors.

11. An organic light-emitting diode, comprising a cathode, an anode, and an organic layer, wherein the organic layer is one or more layers selected from 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 wherein the organic layer contains a platinum complex as described in any one of claims 1-8.

12. The organic light-emitting diode according to claim 11, wherein the platinum complex layer is a light-emitting layer.

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