Mesolytic carbene-copper(i)-carbazole compounds having room temperature phosphorescence properties and methods for their preparation

Abstract

The application belongs to the technical field of luminescent materials, and relates to an interstitial carbene-copper(I)-carbazole compound with room-temperature phosphorescence and a preparation method thereof. The method specifically comprises the following steps: under the atmosphere of an inert gas, taking an interstitial carbene precursor as a starting material, deprotonating the C4 position of the interstitial carbene precursor by sodium bis(trimethylsilyl)amide in the presence of a solvent and cuprous iodide to obtain a double-coordinated interstitial carbene copper(I) complex, and then reacting the double-coordinated interstitial carbene copper(I) complex with a potassium carbazole salt to obtain the interstitial carbene-copper(I)-carbazole compound. The application first uses an interstitial carbene as an organic ligand, develops a novel synthesis method of a linear double-coordinated interstitial carbene-copper(I)-carbazole compound with room-temperature phosphorescence, enriches the types of copper(I) complexes with phosphorescence emission, and realizes fine adjustment of phosphorescence properties by changing the substituent groups of the 2nd carbon atom on the carbene ring.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, and relates to a mesoionic carbene-copper(I)-carbazole compound with room temperature phosphorescence properties and its preparation method. Background Technology

[0002] Organic light-emitting diodes (OLEDs), as a surface light source, possess a series of advantages such as simple fabrication, low driving voltage, and fast response time, and are considered one of the most promising new display and solid-state lighting technologies. To date, most luminescent materials used in OLEDs have closed-shell electronic structures, with their ground state being a singlet state. Therefore, traditional fluorescent materials in OLEDs can only utilize 25% of singlet excitons for emission, while up to 75% of triplet excitons do not emit light due to spin-forbidden conditions. This results in a maximum internal quantum efficiency of only 25% for the device (G. Hong, X. Gan, C. Leonhardt, Z. Zhang, J. Seibert, J. Mbusch, S. (Adv. Mater. 2021, 33, 2005, 630). Therefore, how to improve the utilization rate of excitons to improve the luminous efficiency of OLEDs is a frontier and research challenge in this field.

[0003] Compared to traditional fluorescent molecules, phosphorescent molecules can effectively promote intersystem crossing (ISC) of electrons from singlet to triplet states through strong spin-orbit coupling (SOC) of heavy metal atoms. This allows them to fully utilize all singlet and triplet excitons generated by electrical excitation, thus enabling the internal quantum efficiency of phosphorescent molecules to reach the theoretical upper limit of 100% (J. Lee, H.-F. Chen, T. Batagoda, C. Coburn, PID Jurovich, MET Thompson, SR Forrest, Nat. Mater. 2016, 15, 92; X. Yang, S. Xu, Y. Zhang, C. Zhu, L. Cui, G. Zhou, Z. Chen, Y. Sun, Angew. Chem. Int. Ed. 2023, e202309739). In 1998, Forrest's group reported an electroluminescent device with red phosphorescence emission using platinum complexes as the host dopant. It exhibited high efficiency in singlet and triplet energy transfer (≥90%), with peak external quantum efficiency and internal quantum efficiency reaching 4% and 23%, respectively, demonstrating the potential of such heavy metal complexes in electroluminescent devices (MA Baldo, DFO'Brien, Y. You, A. Shoustikov, S. Sibley, METhompson, SR Forrest, Nature 1998, 395, 151). In 2015, Professor Ji Yun used a tetradentate platinum complex as a luminescent molecule, obtaining an OLED device with a maximum external quantum efficiency of 24% and near-infrared emission, demonstrating the high efficiency advantage of noble metal complexes in OLED device applications (K.-Y.Liao, C.-W.Hsu, Y.Chi, M.-K.Hsu, S.-W.Wu, C.-H.Chang, S.-H.Liu, G.-H.Lee, P.-T.Chou, Y.Hu, N.Robertson, Inorg.Chem. 2015, 54, 4029). Although phosphorescent molecules based on noble metals such as Os, Ir, and Pt have shown considerable performance in the field of light-emitting devices, their large-scale application has always been limited by the high cost and significant environmental pollution of noble metals. Therefore, researching other inexpensive transition metal complex luminescent materials has become an increasingly urgent need.

[0004] Copper(I) complexes, due to their excellent luminescence properties, rich structural diversity, and low cost, hold promise as alternatives to precious metals. Meanwhile, organic ligands are crucial for regulating the luminescence properties of these complexes. Most copper(I) complexes reported in the literature are tri- or tetra-coordinated, but fine-tuning of ligand properties remains a significant challenge (VA Krylova, PID Jurovich, BL Conley, R. Haiges, MT Whited, TJ Williams, MET Thompson, Chem. Commun. 2014, 50, 7176; Y.-E. Kim, J. Kim, JWPark, K. Park, Y. Lee, Chem. Commun. 2017, 53, 2858). Therefore, research on fine-tuning of ligand properties has strong practical application significance for regulating luminescence properties. Summary of the Invention

[0005] The purpose of this invention is to provide a mesoionic carbene-copper(I)-carbazole compound with room temperature phosphorescence properties and its preparation method. More specifically, based on the unique electronic properties of mesoionic carbenes, this invention has successfully constructed a series of mesoionic carbene-copper(I)-carbazole compounds.

[0006] The implementation process of this invention is as follows:

[0007] A mesoionic carbene-copper(I)-carbazole compound, the chemical structural formula of which is shown below:

[0008]

[0009] Where Ar is selected from Polycyclic aromatic hydrocarbons;

[0010] R 1 Selected from hydrogen-based, halogen-based, cyano-based, alkyl-based, and alkoxy-based groups having 1-6 carbon atoms;

[0011] R 2 Selected from hydrogen group, halogen group, cyano group, and -C(O)CH3.

[0012] Furthermore, the polycyclic aromatic hydrocarbon is

[0013] Any one of them.

[0014] A method for preparing a mesoionic carbene-copper(I)-carbazole compound with room temperature phosphorescence properties is as follows: under an inert gas atmosphere, using a mesoionic carbene precursor as a starting material, in the presence of a solvent and cuprous iodide, sodium di(trimethylsilyl)amino is used to deprotonate the C4 position of the mesoionic carbene precursor to obtain a bicoordinated mesoionic carbene copper(I) complex, which is then reacted with potassium carbazole to obtain the mesoionic carbene-copper(I)-carbazole compound.

[0015]

[0016] Furthermore, the solvent is selected from dichloromethane, trichloromethane, toluene, diethyl ether, or tetrahydrofuran.

[0017] Furthermore, the molar ratio of the mesenchymal carbene precursor, cuprous iodide, and sodium di(trimethylsilyl)aminodiaminodioxide is 1:1.05:1.05.

[0018] Furthermore, the molar ratio of the mesonized carbene precursor to the potassium carbazole salt is 1:1.

[0019] The design concept of this invention is based on the principle that finely adjusting the number of coordination groups and ligands is a crucial way to enhance the luminescence properties of copper(I) complexes. Mesoionic carbenes, compared to traditional nitrogen-containing heterocyclic carbenes, possess a stronger electron-donating ability and can form strong metal-carbon bonds with metals, thereby improving the stability of the complex and adjusting the band gaps of singlet and triplet states. Furthermore, mesoionic carbenes offer advantages such as structural diversity, easily adjustable electronic properties and steric hindrance, allowing for fine-tuning of the electronic structure and luminescence properties of metal complexes. Therefore, mesoionic carbenes not only effectively improve the stability of copper(I) complexes but also allow for fine-tuning of the complex's properties by altering the substituent groups on the carbene ring.

[0020] The positive effects of this invention:

[0021] This invention is the first to utilize mesenchymal carbene as an organic ligand, and develops a novel method for synthesizing linear dual-coordinate mesenchymal carbene-copper(I)-carbazole compounds with room temperature phosphorescence properties. This not only enriches the types of phosphorescent copper(I) complexes, but also enables fine-tuning of phosphorescence properties by changing the substituent group on the second carbon atom of the carbene ring. Attached Figure Description

[0022] Figure 1 The 1H NMR spectrum of the meso-ion carbene-copper(I)-carbazole 2a is shown.

[0023] Figure 2 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2a;

[0024] Figure 3The fluorescence spectrum of a toluene solution of meso-carbene-copper(I)-carbazole 2a was obtained under an argon and oxygen atmosphere.

[0025] Figure 4 The 1H NMR spectrum of the meso-ion carbene-copper(I)-carbazole 2b is shown.

[0026] Figure 5 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2b;

[0027] Figure 6 The fluorescence spectrum of a toluene solution of the meso-ion carbene-copper(I)-carbazole 2b was obtained under an argon and oxygen atmosphere.

[0028] Figure 7 The 1H NMR spectrum of the meso-ion carbene-copper(I)-carbazole 2c is shown.

[0029] Figure 8 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2c;

[0030] Figure 9 The fluorescence spectrum of a toluene solution of the meso-ion carbene-copper(I)-carbazole 2c was obtained under an argon and oxygen atmosphere.

[0031] Figure 10 The 1H NMR spectrum of the meso-ion carbene-copper(I)-carbazole 2d is shown.

[0032] Figure 11 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2d;

[0033] Figure 12 The fluorescence spectrum of a toluene solution of meso-carbene-copper(I)-carbazole 2d was obtained under an argon and oxygen atmosphere.

[0034] Figure 13 The 1H NMR spectrum of the meso-ion carbene-copper(I)-carbazole 2e is shown.

[0035] Figure 14 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2e;

[0036] Figure 15 The 1H NMR spectrum of the meso-ion carbene-copper(I)-carbazole 2f is shown.

[0037] Figure 16 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2f;

[0038] Figure 17 The 1H NMR spectrum of carbene-copper(I)-carbazole 2g is shown.

[0039] Figure 18The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole for 2 hours is shown.

[0040] Figure 19 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2i;

[0041] Figure 20 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2j is shown.

[0042] Figure 21 The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2k;

[0043] Figure 22 This is the single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2l. Detailed Implementation

[0044] The present invention will be further described below with reference to the embodiments.

[0045] Example 1: Preparation of mesoionic carbene-copper(I)-carbazole 2a

[0046]

[0047] 2a: Under a nitrogen atmosphere, 700 mg (0.92 mmol) of 1a, 178 mg (0.97 mmol) of sodium bis(trimethylsilyl)aminoacetate, 184 mg (0.97 mmol) of cuprous iodide, and 30 mL of tetrahydrofuran were added sequentially to a 100 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 189 mg (0.92 mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain 594 mg of the orange product 2a, with a yield of 75%. 1HNMR (400MHz, THF-d8): δ7.80(d,J=8.0Hz,2H),7.61(t,J=8.0Hz,1H),7.52(t,J=7.6Hz,1H),7. 43(d,J=8.0Hz,2H),7.39(d,J=8.0Hz,2H),7.36(s,1H),7.24(t,J=7.6Hz,4H),7.07(t,J=7.2Hz 2H),6.96–6.91(m,6H),6.87(d,J=8.0Hz,2H),6.81(d,J=8.8Hz,2H),6.74-6.68(m,4H),2.8 2(sept,2H),2.75(sept,2H),1.38(d,J=6.8Hz,6H),1.30(d,J=6.8Hz,6H),1.07(m,12H)ppm. 13 C NMR (100MHz, THF-d8): δ160.4,151.3,150.6,147.0,145.8,145.8,145.0,137.4,133.0,131.6,131.0,130.7,130.5, 130.3,126.5,125.5,125,4,124.9,123.1,120.0,119.2,115.4,115.2,114.9,29.7,29.6,25.4,25.3,22.9,22.8ppm.

[0048] The 1H NMR spectrum of the mesoionic carbene-copper(I)-carbazole 2a prepared by the above synthesis method is shown in the figure. Figure 1 The proton NMR spectrum showed that the complex can exist independently and stably, and can be isolated, purified, and characterized. The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2a is shown below. Figure 2 .

[0049] Fluorescence performance test:

[0050] The fluorescence spectrum of a toluene solution of the meso-ion carbene-copper(I)-carbazole 2a was obtained under an argon and oxygen atmosphere, see [reference needed]. Figure 3 As shown in the figure, its phosphorescence emission wavelength is 571nm.

[0051] Example 2: Preparation of mesoionic carbene-copper(I)-carbazole 2b

[0052]

[0053] 2b: Under a nitrogen atmosphere, 1.1 g (1.47 mmol) of 1b, 284 mg (1.55 mmol) of sodium bis(trimethylsilyl)aminoacetate, 294 mg (1.55 mmol) of cuprous iodide, and 50 mL of tetrahydrofuran were added sequentially to a 200 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 302 mg (1.47 mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain 1.15 g of the orange product 2b, with a yield of 87%. 1 HNMR (400MHz, THF-d8): δ7.79(d,J=7.6Hz,2H),7.61(t,J=8.0Hz,1H),7.52(t,J=7.6Hz,1H),7 .43(d,J=7.6Hz,2H),7.38(d,J=8.0Hz,2H),7.35(s,1H),7.06–6.97(m,8H),6.92(t,J=8.0Hz,2 H),6.86(d,J=8.0Hz,2H),6.81(d,J=8.8Hz,2H),6.72(t,J=7.6Hz,2H),6.62(d,J=9.2Hz,2H),2 .81(sept,2H),2.74(sept,2H),1.38(d,J=6.8Hz,6H),1.30(d,J=6.8Hz,6H),1.07(m,12H)ppm. 13 C NMR (100MHz, THF-d8): δ162.0,160.5,159.6,151.3,150.7,145.9,145.8,145.0,143.0,143.0,137.4,133.0,131.6,131.0,130 .8,130.5,128.7,128.6,125.5,124.9,123.1,119.2,118.9,117.3,117.1,115.2,114.9,29.7,29.6,25.4,25.3,22.9,22.7ppm.

[0054] The 1H NMR spectrum of the mesoionic carbene-copper(I)-carbazole 2b prepared by the above synthesis method is shown in [reference needed]. Figure 4 The proton NMR spectrum showed that the complex can exist independently and stably, and can be isolated, purified, and characterized. The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2b is shown below. Figure 5 .

[0055] Fluorescence performance test:

[0056] The fluorescence spectrum of a toluene solution of the meso-ion carbene-copper(I)-carbazole 2b was obtained under an argon and oxygen atmosphere, see [reference needed]. Figure 6 As shown in the figure, its phosphorescence emission wavelength is 587nm.

[0057] Example 3: Preparation of mesoionic carbene-copper(I)-carbazole 2c

[0058]

[0059] 2c: Under a nitrogen atmosphere, 290 mg (0.381 mmol) of 1c, 73 mg (0.4 mmol) of sodium bis(trimethylsilyl)aminoacetate, 76 mg (0.4 mmol) of cuprous iodide, and 20 mL of tetrahydrofuran were added sequentially to a 100 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 78 mg (0.381 mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain a pale yellow product, 225 mg of 2c, with a yield of 65%. 1 H NMR (400MHz, THF-d8): δ7.79(d,J=7.6Hz,2H),7.64(t,J=8.0Hz,1H),7.60(d,J=8.8Hz, 4H),7.55(t,J=8.0Hz,1H),7.46(s,2H),7.42(t,J=8.4Hz,3H),7.00(d,J=8.8Hz,4H),6. 97(s,3H),6.93(t,J=8.0Hz,3H),6.87(d,J=8.0Hz,2H),6.73(t,J=7.6Hz,2H),2.81(se pt,2H),2.74(sept,2H),1.39(d,J=6.8Hz,6H),1.32(d,J=6.8Hz,6H),1.08(m,12H)ppm.

[0060] The 1H NMR spectrum of the mesoionic carbene-copper(I)-carbazole 2c prepared by the above synthesis method is shown in the figure. Figure 7 The proton NMR spectrum showed that the complex can exist independently and stably, and can be isolated, purified, and characterized. The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2c is shown below. Figure 8 .

[0061] Fluorescence performance test:

[0062] The fluorescence spectrum of the toluene solution of the mesoionic carbene-copper(I)-carbazole 2c prepared by the above synthesis method was measured under an argon and oxygen atmosphere, as shown in the figure. Figure 9 As shown in the figure, its phosphorescence emission wavelength is 631nm.

[0063] Example 4: Preparation of mesoionic carbene-copper(I)-carbazole 2d

[0064]

[0065] 2d: Under a nitrogen atmosphere, 676 mg (0.91 mmol) of 1d, 176 mg (0.96 mmol) of sodium bis(trimethylsilyl)aminoacetate, 190 mg (0.96 mmol) of cuprous iodide, and 30 mL of tetrahydrofuran were added sequentially to a 100 mL Schlenk tube to obtain a light green solution. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 188 mg (0.91 mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain a light green product, 646 mg of 2d, with a yield of 80%. 1 H NMR (400MHz, THF-d8): δ7.79(d,J=7.6Hz,2H),7.60(t,J=8.0Hz,1H),7.51(t,J=8.0Hz,1H),7.41( d,J=7.6Hz,2H),7.37(d,J=7.6Hz,2H),7.32(s,1H),7.05(d,J=8.0Hz,4H),6.92(t,J=6.8Hz,2H), 6.87–6.82(m,6H),6.76(d,J=9.2Hz,2H),6.71(t,J=7.6Hz,2H),6.60(d,J=9.2Hz,2H),2.81(sept ,2H),2.73(sept,2H),2.25(s,6H),1.37(d,J=6.8Hz,6H),1.30(d,J=6.8Hz,6H),1.07(m,12H)ppm. 13 C NMR (100MHz, THF-d8): δ160.2,151.3,150.9,145.8,145.8,145.2,144.4,137.5,135.2,133.0,131.5,131.0,130.8,130.6, 130.4,126.6,125.5,124.9,123.1,119.2,119.0,115.2,114.9,114.5,100.7,29.7,29.6,25.5,25.3,22.9,22.8,20.7ppm.

[0066] The 1H NMR spectrum of the mesoionic carbene-copper(I)-carbazole 2d prepared by the above synthesis method is shown in the figure. Figure 10 The proton NMR spectrum showed that the complex can exist independently and stably, and can be isolated, purified, and characterized. The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2d is shown below. Figure 11 .

[0067] Fluorescence performance test:

[0068] The fluorescence spectrum of the toluene solution of mesoionic carbene-copper(I)-carbazole 2d prepared by the above synthesis method was obtained by testing under an argon and oxygen atmosphere, as shown in the figure. Figure 12 As shown in the figure, its phosphorescence emission wavelength is 566nm.

[0069] Example 5: Preparation of mesoionic carbene-copper(I)-carbazole 2e

[0070]

[0071] Under a nitrogen atmosphere, 745 mg (0.97 mmol) of 1e, 186 mg (1.01 mmol) of sodium bis(trimethylsilyl)aminoacetate, 193 mg (1.01 mmol) of cuprous iodide, and 30 mL of tetrahydrofuran were added sequentially to a 100 mL Schlenk tube to obtain a light green solution. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 198 mg (0.97 mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to the Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain a light green product, 741 mg of 2e, with a yield of 83%. 1 H NMR (400MHz, THF-d8): δ7.79(d,J=7.6Hz,2H),7.60(t,J=8.0Hz,1H),7.51(t,J=7.6Hz,1H) ,7.41(d,J=7.6Hz,2H),7.37(d,J=8.0Hz,2H),7.30(s,1H),6.94–6.90(m,6H),6.87(d,J=8. 0Hz,2H),6.82(d,J=8.8Hz,4H),6.75–6.70(m,4H),6.50(d,J=8.8Hz,2H),3.72(s,6H),2.82 (sept,2H),2.74(sept,2H),1.37(d,J=6.8Hz,6H),1.30(d,J=6.8Hz,6H),1.07(m,12H)ppm.

[0072] 13C NMR (100MHz, THF-d8): δ160.1,158.2,151.4,.151.3,145.9,145.8,145.4,139.4,137.6,133.1,131.5,130.9,130.5,130.3 ,128.3,125.5,124.9,123.4,123.1,119.2,117.2,115.6,115.3,114.9,113.3,55.4,29.7,29.6,25.4,25.3,23.0,22.8ppm.

[0073] The 1H NMR spectrum of the meso-ion carbene-copper(I)-carbazole 2e, Figure 13 The proton NMR spectrum showed that the complex can exist independently and stably, and can be isolated, purified, and characterized. The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2e is shown in [reference needed]. Figure 14 .

[0074] Example 6: Preparation of mesoionic carbene-copper(I)-carbazole 2f

[0075]

[0076] 2f: Under a nitrogen atmosphere, 200 mg (0.32 mmol) of 1f, 62.4 mg (0.34 mmol) of sodium bis(trimethylsilyl)aminoacetate, 64.8 mg (0.34 mmol) of cuprous iodide, and 30 mL of tetrahydrofuran were added sequentially to a 100 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 66 mg (0.32 mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain a pale yellow product, 196 mg of 2f, with a yield of 85%. 1H NMR (400MHz, CDCl3): δ8.02(d,J=7.6Hz,2H),7.63(t,J=8.0Hz,1H),7.56(t,J=8.0Hz,1H) ,7.43(d,J=8.8Hz,2H),7.36(d,J=7.6Hz,2H),7.33(d,J=7.6Hz,2H),7.19(s,1H),7.13(t ,J=7.2Hz,2H),7.05(d,J=8.8Hz,2H),7.01(d,J=8.4Hz,2H),6.94(t,J=7.6Hz,2H),2.65( sept,2H),2.59(sept,2H),1.39(d,J=6.8Hz,6H),1.33(d,J=6.8Hz,6H),1.01(m,12H)ppm.

[0077] The 1H NMR spectrum of the mesoionic carbene-copper(I)-carbazole 2f prepared by the above synthesis method is shown in the figure. Figure 15 The proton NMR spectrum showed that the complex can exist independently and stably, and can be isolated, purified, and characterized. The single-crystal diffraction pattern of the meso-ion carbene-copper(I)-carbazole 2f is shown in [reference needed]. Figure 16 .

[0078] Example 7: Preparation of 2g of mesenchymal carbene-copper(I)-carbazole

[0079]

[0080] 2g: Under a nitrogen atmosphere, 1g (189mg, 0.31mmol), 59.6mg (0.33mmol), sodium bis(trimethylsilyl)aminoacetate, 61.9mg (0.33mmol), and 30mL of tetrahydrofuran were added sequentially to a 100mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 hours. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 64mg (0.31mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 hours. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain 2g (181mg) of a pale yellow product, with a yield of 82%. 1H NMR (400MHz, CDCl3): δ8.01(d,J=7.6Hz,2H),7.59(t,J=8.0Hz,1H),7.52(t,J= 7.6Hz,1H),7.34(d,J=8.0Hz,2H),7.30(d,J=7.6Hz,2H)7.15–7.11(m,3H),7.0 3(d,J=8.0Hz,2H),6.97–6.92(m,4H),6.86(d,J=8.0Hz,2H),2.68(sept,2H),2 .62(sept,2H),1.39(d,J=6.8Hz,6H),1.32(d,J=6.8Hz,6H),1.04(m,12H)ppm.

[0081] The 1H NMR spectrum of 2g of meso-ion carbene-copper(I)-carbazole prepared by the above synthesis method is shown in the figure. Figure 17 The proton NMR spectrum showed that the complex could exist independently and stably, and could be separated, purified and characterized.

[0082] Example 8: Preparation of mesenchymal carbene-copper(I)-carbazole for 2 hours

[0083]

[0084] 2h: Under a nitrogen atmosphere, 100 mg (0.15 mmol) of 1h sodium chloride, 29 mg (0.16 mmol) of sodium bis(trimethylsilyl)aminocyanate, 30 mg (0.16 mmol) of cuprous iodide, and 30 mL of tetrahydrofuran were added sequentially to a 100 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 31 mg (0.15 mmol) of potassium carbazole was added to the supernatant, and the reaction was continued for 16 h. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected and concentrated. Hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with hexane, and dried to obtain a pale yellow product, 81 mg of 2h sodium chloride, with a yield of 70%.

[0085] The single-crystal diffraction pattern of the mesoionic carbene-copper(I)-carbazole 2h prepared by the above synthesis method is shown in the figure. Figure 18 .

[0086] Example 9: Preparation of mesoionic carbene-copper(I)-carbazole 2i

[0087]

[0088] 2i: Under a nitrogen atmosphere, 1i 50mg (8.53×10) was sequentially added. -2 mmol), sodium bis(trimethylsilyl)amino 16.4 mg (8.96 × 10⁻⁶) -2mmol), cuprous iodide 17.1 mg (8.96 × 10⁻⁶) -2 1 mmol) and 20 mL of diethyl ether were added to a 50 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 hours. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 17.5 mg (8.53 × 10⁻⁶) of potassium carbazole was added to the supernatant. -2 The reaction was continued for 16 h. After the reaction was completed, the mixture was centrifuged, the supernatant was collected and concentrated, n-hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with n-hexane, and dried to give 47 mg of the pale yellow product 2i, with a yield of 75%. The single-crystal diffraction pattern of the mesoionic carbene-copper(I)-carbazole 2i prepared by the above synthesis method is shown in [Figure 1]. Figure 19 .

[0089] Example 10 Preparation of mesoionic carbene-copper(I)-carbazole 2j

[0090]

[0091] 2j: Under a nitrogen atmosphere, 1j 50mg (7.76×10) was added sequentially. -2 mmol), sodium bis(trimethylsilyl)amino 15mg (8.15×10 -2 mmol), cuprous iodide 16mg ((8.15×10) -2 1 mmol) and 20 mL of toluene were added to a 50 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 hours. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 16 mg (7.76 × 10⁻⁶ mmol) of carbazole potassium salt was added to the supernatant. -2 The reaction was continued for 16 hours (mmol). After the reaction was completed, the mixture was centrifuged, the supernatant was collected and concentrated, n-hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with n-hexane, and dried to give 49 mg of the pale yellow product 2j, with a yield of 80%. The single-crystal diffraction pattern of the mesoionic carbene-copper(I)-carbazole 2j prepared by the above synthesis method is shown in [Figure 1]. Figure 20 .

[0092] Example 11 Preparation of mesoionic carbene-copper(I)-carbazole 2k

[0093]

[0094] 2k: Under a nitrogen atmosphere, 1k 50mg (8.41×10) was sequentially added. -2 mmol), sodium bis(trimethylsilyl)amino 16mg (8.83×10 -2 mmol), cuprous iodide 17mg (8.83×10 mmol), -21 mmol) and 30 mL of chloroform were added to a 100 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 hours. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 17 mg (8.41 × 10⁻⁶) of potassium carbazole was added to the supernatant. -2 The reaction was continued for 16 h. After the reaction was completed, the mixture was centrifuged, the supernatant was collected and concentrated, n-hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with n-hexane, and dried to give a pale yellow product of 2k47 mg, with a yield of 75%. The single-crystal diffraction pattern of the mesoionic carbene-copper(I)-carbazole 2k prepared by the above synthesis method is shown in [Figure 1]. Figure 21 .

[0095] Example 12 Preparation of mesoionic carbene-copper(I)-carbazole 2l

[0096]

[0097] 2L: Under a nitrogen atmosphere, 1L of 50mg (7.76×10) was added sequentially. -2 mmol), sodium bis(trimethylsilyl)amino 15mg (8.15×10 -2 mmol), cuprous iodide 16mg ((8.15×10) -2 1 mmol) and 20 mL of dichloromethane were added to a 50 mL Schlenk tube to obtain a pale yellow solution. The mixture was stirred at room temperature for 8 hours. After the reaction was complete, the mixture was centrifuged, and the supernatant was collected. 16 mg (7.76 × 10⁻⁶) of carbazole potassium salt was added to the supernatant. -2 The reaction was continued for 16 h. After the reaction was completed, the mixture was centrifuged, the supernatant was collected and concentrated, n-hexane was added to a Schlenk tube, and the mixture was stirred vigorously. The mixture was filtered, washed with n-hexane, and dried to obtain 2147 mg of a light yellow product, with a yield of 77%. The single-crystal diffraction pattern of the mesoionic carbene-copper(I)-carbazole 21 prepared by the above synthesis method is shown in [Figure 1]. Figure 22 .

[0098] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention.

Claims

1. A mesoionic carbene-copper(I)-carbazole compound, characterized in that, The chemical structural formula is shown below: ； Where Ar is selected from , ; R 1 Selected from hydrogen-based, halogen-based, cyano-based, alkyl-based, and alkoxy-based groups having 1-6 carbon atoms; R 2 Selected from hydrogen group, halogen group, cyano group, and -C(O)CH3.

2. The method for preparing the mesoionic carbene-copper(I)-carbazole compound according to claim 1, characterized in that: In an inert gas atmosphere, using a meso-carbene precursor as a starting material, in the presence of a solvent and cuprous iodide, sodium di(trimethylsilyl)aminodi ... 。 3. The method according to claim 2, characterized in that: The solvent is selected from dichloromethane, trichloromethane, toluene, diethyl ether, or tetrahydrofuran.

4. The method according to claim 2, characterized in that: The molar ratio of the methanogenic carbene precursor, cuprous iodide, and sodium di(trimethylsilyl)aminodiaminodioxide is 1:1.05:1.

05.

5. The method according to claim 2, characterized in that: The molar ratio of the methanogenic carbene precursor to potassium carbazole is 1:1.

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