Discrete gold (I) sulfur cluster cage based on N-heterocyclic carbene protection and preparation method thereof

Abstract

The invention discloses a discrete gold (I) sulfur cluster cage based on N-heterocyclic carbene protection and a preparation method thereof, and belongs to the technical field of chemical synthesis. The preparation method comprises the following steps: reacting a 1, 3, 5-triazine compound or a 1, 3, 5-substituted benzene ring compound with a 1-alkyl imidazole compound to prepare tridentate imidazolium salt, then reacting tridentate imidazolium with silver oxide and Au (THT) Cl in sequence to prepare the tridentate imidazole gold carbene complex, and finally reacting with H2S to prepare the tridentate imidazole gold carbene complex. The invention provides a method for realizing better encapsulation of active substances and neutral objects by regulating and controlling the conformation of NHC ligands and utilizing a closed cavity of a discrete gold (I) sulfide cluster cage, solves the problem of confirmation of fourth group IV methylated crystal structures under environmental pressure, provides important guidance for accurately constructing a novel multi-core discrete gold (I) sulfide cluster assembly, and provides a new method for accurately constructing the multi-core discrete gold (I) sulfide cluster assembly. And a new way is opened up for exploring further host-guest interaction in the assembly.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemical synthesis, in particular to a discrete gold(I) chalcogen cluster cage based on N-heterocyclic carbene protection and a preparation method thereof. BACKGROUND

[0002] Discrete metal-organic cages with well-defined geometry and specific cavities constructed through coordination-driven self-assembly have been extensively studied. Their unique structural properties make them have high application value in the fields of host-guest chemistry, drug delivery, separation and adsorption, stabilization of active substances, and catalysis. To our knowledge, although traditional metal-organic cage design mainly relies on single metal ions as connecting nodes between ligands, the use of metal clusters or multi-core vertices has recently become a powerful strategy for constructing metal cages. Compared with single metal vertices, metal clusters provide more diverse connection modes and a variety of coordination numbers and geometries, thus enabling higher structural complexity.

[0003] The introduction of metal cluster building blocks into organic metal assembly systems can generate supramolecular assemblies with unique structures, and the metal Complexes of metal-bound clusters often exhibit unique properties different from mononuclear metals. Among them, the metal M3 units connected by metal bonds form [( μ 3-S)Au3] + Clusters are the smallest building blocks of polynuclear gold(I) chalcogenide complexes, and can also serve as vertices of discrete gold(I) chalcogenide polyhedra. Due to the presence of goldophilic interactions, many aggregated polynuclear gold(I) chalcogenide complexes protected by bidentate phosphine ligands have been reported, and their photophysical properties and complex structures have been fully characterized. However, there are few reports on the assembly of discrete gold(I) chalcogenide cage structures. At the same time, these gold(I) chalcogenide complexes are usually unstable in solution and are prone to structural transformation under external stimuli, which limits their application exploration in solution. Therefore, the design and synthesis of discrete gold(I) chalcogenide cages stable in solution is still a challenging but significant goal, which will help to study their potential host-guest properties under solution conditions.

[0004] N-heterocyclic carbene (NHC) ligands, as strong coordinating ligands in organometallic chemistry, can form stable metal C C NHC bonds (M μ C ) with metal centers due to their excellent σ-donating properties. In recent years, by rationally designing NHC ligands to coordinate with single metals, a series of two-dimensional (2D) and three-dimensional (3D) organometallic supramolecular assemblies have been successfully constructed. Based on these advances, we use [( μ 3-S)Au3]+ Units replacing single-metal nodes and assembling with NHC ligands to construct novel supramolecular structures provide a basis for [( μ 3-S)Au3] + Unit design and construction of novel cluster-based supramolecular assemblies offer a strategy. However, the applications of such assemblies in host-guest chemistry have been rarely explored. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a discrete gold (I) sulfur cluster cage based on nitrogen heterocyclic carbene protection and its preparation method.

[0006] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: In a first aspect, the present invention provides a discrete gold(I)sulfur cluster cage based on nitrogen heterocyclic carbene protection, with a structural formula as shown in any one of formulas I-IV; Formula I: ; In Formula I, R includes any one of C1-C3 alkyl groups; X includes any one of halogen groups, OTf, PF6, SbF6, BF4, and ReO4; Formula II: ; In Formula II, R includes any one of C1-C3 alkyl groups; X includes any one of halogen groups, OTf, PF6, SbF6, BF4, and ReO4; Formula III: ; In Formula III, R includes any one of C1-C3 alkyl groups; X includes any one of halogen groups, OTf, PF6, SbF6, BF4, and ReO4; Formula IV: ; In formula IV, R includes any one of C1-C4 alkyl groups; X includes any one of halogen groups, OTf, PF6, SbF6, BF4, and ReO4.

[0007] A second aspect of the present invention provides a method for preparing a discrete gold (I) sulfur cluster cage based on nitrogen heterocyclic carbene protection as shown in Formula I, wherein the method for preparing the discrete gold (I) sulfur cluster cage shown in Formula I includes the following steps: S101. Tridentate imidazole onium salt is prepared by reacting 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine and 1-alkylimidazolium compound in a solvent. S102. The tridentate imidazole onium salt obtained in S101 and silver oxide are reacted in a solvent, and then Au(THT)Cl is added to the solvent to continue the reaction to obtain the tridentate imidazole gold carbene complex. S103. The tridentate imidazole gold carbene complex obtained in S102 was reacted with H2S in a solvent to prepare a discrete gold(I) sulfur cluster cage with X as Cl. S104. The discrete gold (I) sulfur cluster cage with X being Cl obtained in S103 is reacted with a salt of any one of OTf, PF6, SbF6, BF4 and ReO4 in a solvent to prepare discrete gold (I) sulfur cluster cages with X being any one of OTf, PF6, SbF6, BF4 and ReO4 respectively.

[0008] Further, in S101, the 1-alkylimidazolium compound includes any one of 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, and 1-butylimidazolium; the molar ratio of 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine to the 1-alkylimidazolium compound is 1:(3-9); the reaction temperature is 100-150 °C, and the reaction time is 20-30 h.

[0009] Furthermore, the reaction solvent in S101 is N,N-dimethylformamide.

[0010] Furthermore, in S102, the molar ratio of tridentate imidazole onium salt, silver oxide, and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction is carried out at room temperature for 10-15 h; the reaction continues at room temperature for 10-15 h.

[0011] Furthermore, the solvent for the reaction in S102 is acetonitrile; the solvent for the continued reaction is diethyl ether.

[0012] Furthermore, in S103, the reaction temperature is room temperature and the reaction time is 10-15 h.

[0013] Furthermore, in S103, the reaction solvent is a mixed solvent composed of dichloromethane, ethanol and pyridine in a volume ratio of 1:1:1.

[0014] Furthermore, in S104, the molar ratio of X, which is a discrete gold (I) sulfur cluster cage of Cl, to any one of the salts of OTf, PF6, SbF6, BF4, and ReO4 is 1:(3-12); the reaction temperature is room temperature and the time is 10-15 h.

[0015] Furthermore, in S104, the reaction solvent is methanol.

[0016] A third aspect of the present invention provides a method for preparing a discrete gold(I)sulfur cluster cage based on nitrogen heterocyclic carbene protection as shown in Formula II, wherein the method for preparing the discrete gold(I)sulfur cluster cage shown in Formula II includes the following steps: S201. 1,3,5-tris(4-bromomethylphenyl)benzene and 1-alkylimidazolium compound are reacted in a solvent, and then reacted with NH4PF6 in a solvent to obtain tridentate imidazolium salt; S202. The tridentate imidazole onium salt obtained in S201 and silver oxide are reacted in a solvent, and then Au(THT)Cl is added to the solvent to continue the reaction to obtain the tridentate imidazole gold carbene complex. S203: The tridentate imidazole gold carbene complex obtained in S202 was reacted with H2S in a solvent to prepare a discrete gold(I) sulfur cluster cage with X as Cl. S204. The discrete gold (I) sulfur cluster cage with X being Cl obtained from S203 is reacted with a salt of any one of OTf, PF6, SbF6, BF4 and ReO4 in a solvent to prepare discrete gold (I) sulfur cluster cages with X being any one of OTf, PF6, SbF6, BF4 and ReO4 respectively.

[0017] Further, in S201, the 1-alkylimidazolium compound includes any one of 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, and 1-butylimidazolium; the molar ratio of 1,3,5-tris(4-bromomethylphenyl)benzene, the 1-alkylimidazolium compound, and NH4PF6 is 1:(3-9):(5-15); the reaction temperature is 100-150 °C, and the time is 20-30 h; the reaction continues at room temperature for 10-15 h.

[0018] Furthermore, the solvent used for the reaction in S201 is N,N-dimethylformamide; the solvent for the continued reaction is methanol.

[0019] Furthermore, in S202, the molar ratio of tridentate imidazole onium salt, silver oxide, and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction is carried out at room temperature for 10-15 h; the reaction continues at room temperature for 10-15 h.

[0020] Furthermore, the solvent used for the reaction in S202 is acetonitrile; the solvent used for the continued reaction is diethyl ether.

[0021] Furthermore, in S203, the reaction temperature is room temperature and the time is 10-15 h.

[0022] Furthermore, in S203, the reaction solvent is a mixed solvent composed of dichloromethane, ethanol and pyridine in a volume ratio of 1:1:1.

[0023] Furthermore, in S204, the molar ratio of X, which is a discrete gold (I) sulfur cluster cage of Cl, to any one of the salts of OTf, PF6, SbF6, BF4, and ReO4 is 1:(3-12); the reaction temperature is room temperature and the time is 10-15 h.

[0024] Furthermore, in S204, the reaction solvent is methanol.

[0025] A fourth aspect of the present invention provides a method for preparing a discrete gold(I)sulfur cluster cage based on nitrogen heterocyclic carbene protection as shown in Formula III, wherein the method for preparing the discrete gold(I)sulfur cluster cage shown in Formula III includes the following steps: S301. 1,3,5-tris[4-(4-bromomethyl)phenyl]phenyl]benzene and 1-alkylimidazolium compound are reacted in a solvent, and then reacted with NH4PF6 in a solvent to prepare tridentate imidazolium salt; S302. The tridentate imidazole onium salt obtained in S301 and silver oxide are reacted in a solvent, and then Au(THT)Cl is added to the solvent to continue the reaction to obtain the tridentate imidazole gold carbene complex. S303: The tridentate imidazole gold carbene complex obtained in S302 was reacted with H2S in a solvent to prepare a discrete gold(I) sulfur cluster cage with X as Cl. S304. The discrete gold (I) sulfur cluster cage with X being Cl obtained from S303 is reacted with a salt of any one of OTf, PF6, SbF6, BF4 and ReO4 in a solvent to obtain discrete gold (I) sulfur cluster cages with X being any one of OTf, PF6, SbF6, BF4 and ReO4 respectively.

[0026] Further, in S301, the 1-alkylimidazolium compound includes any one of 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, and 1-butylimidazolium; the molar ratio of 1,3,5-tris[4-(4-bromomethyl)phenyl]phenyl]benzene, the 1-alkylimidazolium compound, and NH4PF6 is 1:(3-9):(5-15); the reaction is carried out at a temperature of 100-150 °C for 20-30 h; the reaction continues at room temperature for 10-15 h.

[0027] Furthermore, the solvent used for the reaction in S301 is N,N-dimethylformamide; the solvent used for the further reaction is methanol.

[0028] Furthermore, in S302, the molar ratio of tridentate imidazole onium salt, silver oxide, and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction is carried out at room temperature for 10-15 h; the reaction continues at room temperature for 10-15 h.

[0029] Furthermore, the solvent used for the reaction in S302 is acetonitrile; the solvent used for the continued reaction is diethyl ether.

[0030] Furthermore, in S303, the reaction temperature is room temperature and the time is 10-15 h.

[0031] Furthermore, in S303, the reaction solvent is a mixed solvent composed of dichloromethane, ethanol and pyridine in a volume ratio of 1:1:1.

[0032] Furthermore, in S304, the molar ratio of X, which is a discrete gold (I) sulfur cluster cage of Cl, to any one of the salts of OTf, PF6, SbF6, BF4, and ReO4 is 1:(3-12); the reaction temperature is room temperature and the time is 10-15 h.

[0033] Furthermore, in S304, the reaction solvent is methanol.

[0034] A fifth aspect of the present invention provides a method for preparing a discrete gold(I)sulfur cluster cage based on nitrogen heterocyclic carbene protection as shown in Formula IV, wherein the method for preparing the discrete gold(I)sulfur cluster cage shown in Formula IV includes the following steps: S401. 2,4,6-tris(4'-(bromomethyl)-[1,1'-diphenyl]-4-yl)-1,3,5-triazine and 1-alkylimidazolium compound are reacted in a solvent, and then reacted with NH4PF6 in a solvent to prepare tridentate imidazolium salt; S402. The tridentate imidazole onium salt obtained in S401 and silver oxide are reacted in a solvent, and then Au(THT)Cl is added to the solvent to continue the reaction to obtain the tridentate imidazole gold carbene complex. S403: The tridentate imidazole gold carbene complex obtained in S402 is reacted with H2S in a solvent to prepare a discrete gold(I) sulfur cluster cage with X as Cl. S404. The discrete gold (I) sulfur cluster cage with X being Cl obtained from S403 is reacted with a salt of any one of OTf, PF6, SbF6, BF4 and ReO4 in a solvent to obtain discrete gold (I) sulfur cluster cages with X being any one of OTf, PF6, SbF6, BF4 and ReO4 respectively.

[0035] Further, in S401, the 1-alkylimidazolium compound includes any one of 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, and 1-butylimidazolium; the molar ratio of 2,4,6-tris(4'-(bromomethyl)-[1,1'-diphenyl]-4-yl)-1,3,5-triazine, the 1-alkylimidazolium compound, and NH4PF6 is 1:(2-9):(5-15); the reaction is carried out at a temperature of 100-150 °C for 20-30 h; the reaction continues at room temperature for 10-15 h.

[0036] Furthermore, the solvent used for the reaction in S401 is N,N-dimethylformamide; the solvent for the continued reaction is methanol.

[0037] Furthermore, in S402, the molar ratio of tridentate imidazole onium salt, silver oxide, and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction is carried out at room temperature for 10-15 h; the reaction is continued at room temperature for 10-15 h.

[0038] Furthermore, the solvent used for the reaction in S402 is acetonitrile; the solvent used for the continued reaction is diethyl ether.

[0039] Furthermore, in S403, the reaction temperature is room temperature and the time is 10-15 h.

[0040] Furthermore, in S403, the reaction solvent is a mixed solvent composed of dichloromethane, ethanol and pyridine in a volume ratio of 1:1:1.

[0041] Furthermore, in S404, the molar ratio of X, which is a discrete gold (I) sulfur cluster cage of Cl, to any one of the salts of OTf, PF6, SbF6, BF4, and ReO4 is 1:(3-12); the reaction temperature is room temperature and the time is 10-15 h.

[0042] Furthermore, in S404, the reaction solvent is methanol.

[0043] In a sixth aspect, the present invention provides a tridentate imidazole gold carbene complex for synthesizing the above-mentioned discrete gold(I) sulfur cluster cage based on nitrogen heterocyclic carbene protection, the chemical structural formula of which is shown in Formulas V-VIII: Formula V: ; In formula V, R includes any one of C1-C4 alkyl groups; Formula VI: ; In Formula VI, R includes any one of C1-C4 alkyl groups; Equation VII: ; In formula VII, R includes any one of C1-C4 alkyl groups; Formula VIII: ; In formula VIII, R includes any one of C1-C4 alkyl groups.

[0044] Furthermore, the discrete gold(I)-sulfur cluster cages shown in formulas I-IV are synthesized sequentially from the tridentate imidazole gold carbene complexes shown in formulas V-VIII.

[0045] Furthermore, the tridentate imidazole kilotone complexes shown in formulas V-VIII are synthesized sequentially via S102, S202, S302, and S402.

[0046] The present invention has the following beneficial effects: This invention designs and synthesizes NHC ligands of different sizes and [( μ 3-S)Au3] + The modular assembly of discrete gold(I) sulfide cluster metal-organic cages with high stability and complex topology provides a method for effectively encapsulating some reactive substances and neutral guests by controlling the conformational flexibility of NHC ligands and utilizing the inherent closed cavity of discrete gold(I) sulfide cluster cages. It also solves the problem of confirming the crystal structure of group IV methylation under environmental pressure. This not only provides important guidance for the precise construction of novel multinuclear discrete gold(I) sulfide cluster assemblies, but also opens up new avenues for exploring further host-guest interactions in such assemblies. Attached Figure Description

[0047] Figure 1 Schematic diagrams of the construction of discrete gold(I) sulfur cluster cages with different topologies; Figure 2 In the test case 1 H NMR spectrum, 1 The results of 1H DOSY spectroscopy and HR-ESI mass spectrometry characterization are shown, where (a) is the C14 of the tridentate imidazole gold carbene complex. 1 1H NMR spectra, (b)-(c) are discrete gold(I) sulfur cluster cages d14, respectively. 1 H NMR spectra and 1 HR-ESI mass spectra of discrete gold(I)sulfur cluster cages d14 and selected cations [d14] are shown in (d). 4PF6] 4+ and [d14] 3PF6] 3+ Isotope distribution; Figure 3 The results of X-ray single-crystal diffraction characterization in the experimental example are shown. (a) is the cationic part of the discrete gold(I) sulfur cluster cage d14 crystal structure, (b) is the center distance of the four metal clusters Au3 in the discrete gold(I) sulfur cluster cage d14, (c) is the dihedral angle between adjacent benzene rings in the discrete gold(I) sulfur cluster cage d14, and (d) is a view of the internal volume of the discrete gold(I) sulfur cluster cage d14 and its aliphatic units in the cavity part calculated by VOIDOO. Orange-yellow represents Au, yellow represents S, blue represents N, gray represents C, and white represents H. Figure 4 A schematic diagram of the crystal structure of tetramethylgermanium encapsulated in a discrete gold(I)sulfur cluster cage d14. Detailed Implementation

[0048] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0049] Example 1: A method for preparing discrete gold(I)sulfur cluster cages based on nitrogen heterocyclic carbene protection (a schematic diagram of the construction of discrete gold(I)sulfur cluster cages is shown in Figure 1). Figure 1 (As shown), including the following steps: Synthesis of S101 and tridentate imidazole salt b2 The synthetic chemical reaction formula is shown below:

[0050] Specifically, the following steps are included: First, add 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine a2 (500 mg, 0.85 mmol, according to literature) to a 100 mL Schlenk reaction tube. Org. Lett 2016, 18, 3394 3397 was prepared, and 1-ethylimidazole (491 mg, 5.11 mmol) was added to the mixture. N,N-dimethylformamide (DMF, 10 mL) was added, and the resulting mixture was reacted at 120 °C for 12 hours. After cooling to room temperature, the reaction solution was concentrated to 2 mL, and ethyl acetate (20 mL) solution was added to the above reaction. A large amount of white flocculent precipitate was precipitated. Finally, the solid was collected by filtration, washed with ethyl acetate (20 mL), and dried under vacuum to obtain tridentate imidazole onium salt b2, with a yield of 685 mg (0.78 mmol) and a yield of 92%.

[0051] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, DMSO- d 6): δ = 9.57 (s, 3H), 8.74 (d, J = 8.4 Hz, 6H), 7.94 (d, J = 8.0 Hz, 6H), 7.73 (d, J = 8.0 Hz, 6H), 5.65 (s, 6H), 4.26 (q, J =7.2 Hz, 6H), 1.45 (t, J= 7.2 Hz, 9H) ppm. 13 C{ 1 H} NMR (100 MHz, DMSO- d 6): δ = 170.7, 139.8, 136.2, 135.5, 129.3,129.0, 122.64, 122.63, 51.5, 44.4, 15.0 ppm. HRMS (ESI, positive ions): m / z = 212.1168 (calcd for [b2-3Br] 3+ 212.1182), 358.6339 (calcd for [b2-2Br] 2+ 358.6359). Synthesis of S102, tridentate imidazole kilotonide complex C2 The synthetic chemical reaction formula is shown below:

[0052] Specifically, the following steps are included: First, tridentate imidazole onium salt b2 (105 mg, 0.12 mmol) and silver oxide (55 mg, 0.24 mmol) were weighed into a 50 mL round-bottom flask. Acetonitrile (10 mL) was added as a solvent to the reaction mixture, and the reaction mixture was stirred at room temperature for 12 hours in the dark. After the reaction was completed, the solvent was removed. Then, Au(THT)Cl (119 mg, 0.37 mmol) and dichloromethane (10 mL) were added as solvents to the above reaction mixture, and the reaction mixture was stirred at room temperature in the dark for 12 hours. The mixture was then slowly filtered through a diatomaceous earth mat to obtain a clear filtrate. Finally, the filtrate was concentrated to 1 mL, and diethyl ether (10 mL) was added. A white precipitate was immediately formed. The precipitate was collected by filtration, washed with diethyl ether (10 mL), and dried under vacuum to obtain gold carbene complex c2, with a yield of 128 mg (0.096 mmol), representing a yield of 80%.

[0053] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, CDCl3): δ = 8.41 (d, J = 8.0 Hz, 6H), 7.40 (d, J = 8.0Hz, 6H), 7.03 (m, 6H), 5.40 (s, 6H), 4.28 (q, J= 7.2 Hz, 6H), 1.50 (t, J = 7.2Hz, 9H) ppm. 13 C{ 1 ¹H NMR (100 MHz, CDCl₃): δ = 170.58, 170.53, 139.9, 136.0, 129.6,128.1, 121.2, 120.9, 54.8, 46.8, 16.7 ppm. HRMS (ESI, positive ions): m / z = 1098.1941 (calcd for [c2+Na+KH] 1+ 1098.2109). Synthesis of S103 and discrete gold(I)sulfur cluster cage d2 The synthetic chemical reaction formula is shown below:

[0054] Specifically, the following steps are included: First, the tridentate gold carbene complex c2 (25 mg, 0.017 mmol) was dissolved in a 3 mL mixture of dichloromethane, ethanol, and pyridine in a volume ratio of 1:1:1. Freshly generated H2S gas was then bubbled into the solution, and the reaction was stirred at room temperature for 12 hours. The solution changed from colorless and clear to pale yellow and turbid. After the reaction was complete, the solvent was removed under vacuum to obtain a pale yellow solid. The solid was washed with 10 mL of water and dried under vacuum to obtain discrete gold(I)sulfur cluster cage d2, with a yield of 357 mg (0.0045 mmol), representing a yield of 79%.

[0055] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (600 MHz, DMSO- d 6): δ = 8.18 (d, J = 7.9 Hz, 6H), 8.01, (m, 4H),7.71(m, 12H), 7.63 (m, 14H), 7.17 (m, 6H), 6.96 (d, J = 7.5 Hz, 6H), 6.70 (d, J = 8.0 Hz, 6H), 6.18 (d, J = 12.9 Hz, 2H), 5.64 (d, J= 14.5 Hz, 8H), 5.35 (d, J = 14.9 Hz, 6H), 5.30 (m, 2H), 4.41 (m, 8H), 4.25 (m, 6H), 4.18 (m, 2H), 3.48(m, 2H), 1.55 (t, J = 7.1 Hz, 14H), 1.36 (t, J = 7.1 Hz, 8H), 1.08 (t, J = 7.3Hz, 5H) ppm. HRMS (ESI, positive ions): m / z = 1256.5738 (calcd for [d2-3Cl] 3+ 1256.5383). Example 2: A method for preparing discrete gold(I)sulfur cluster cages based on nitrogen heterocyclic carbene protection (a schematic diagram of the construction of discrete gold(I)sulfur cluster cages is shown in Figure 1). Figure 1 (As shown), including the following steps: Synthesis of S201 and tridentate imidazole salt b8 The synthetic chemical reaction formula is shown below:

[0056] Specifically, the following steps are included: First, add 1,3,5-tris(4-bromomethylphenyl)benzene a8 (211 mg, 0.36 mmol, according to literature) to a 50 mL Schlenk reaction tube. J. Incl. Phenom. Macrocycl. Chem 2015, 81, 141 152) 1-Butylimidazole (268 mg, 2.2 mmol) was added to N,N-dimethylformamide (DMF, 5 mL) as a solvent, and the resulting mixture was reacted at 120 °C for 24 hours. After cooling to room temperature, the reaction solution was concentrated to 2 mL, and ethyl acetate (20 mL) solution was added to the above reaction. A large amount of white flocculent precipitate precipitated. The solid was collected by filtration, washed with ethyl acetate (20 mL), and dried under vacuum. The resulting solid was then dissolved in 10 mL of methanol solution, and 5 mL of methanol solution containing NH4PF6 (587 mg, 3.6 mmol) was added. A white precipitate precipitated immediately, and the reaction was stirred at room temperature for 12 hours. Finally, the precipitate was collected by filtration, washed with methanol (20 mL), and dried under vacuum to obtain tridentate imidazole onium salt b8, with a yield of 357 mg (0.31 mmol), a yield of 86%.

[0057] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, DMSO- d 6): δ = 9.36 (s, 3H), 7.94 (m, 9H), 7.84 (d, J =12.2 Hz, 6H), 7.56 (d, J = 8.0 Hz, 6H), 5.49 (s, 6H), 4.20 (t, J = 7.3 Hz, 6H),1.80 (m, 6H), 1.28 (m, 6H), 0.92 (t, J = 7.3 Hz, 9H) ppm. 13 C{ 1 H} NMR (100 MHz, DMSO- d 6): δ = 141.0, 140.3, 136.2, 134.4, 129.0,127.8, 124.8, 122.9, 122.6, 51.7, 48.8, 31.3, 18.8, 13.3 ppm. HRMS (ESI, positive ions): m / z = 1007.3497 (calcd for [b8-PF6] + 1007.3923). Synthesis of S202 and C8 of the tridentate imidazole gold carbene complex The synthetic chemical reaction formula is shown below:

[0058] Specifically, the following steps are included: First, tridentate imidazole onium salt B8 (53 mg, 0.046 mmol), silver oxide (21 mg, 0.092 mmol), and tetramethylammonium chloride (31 mg, 0.28 mmol) were weighed into a 25 mL round-bottom flask. Dichloromethane (5 mL) and acetonitrile (5 mL) were added as solvents. The reaction mixture was stirred at room temperature for 12 hours in the dark. After the reaction was complete, the solvent was removed. Then, Au(THT)Cl (45 mg, 0.14 mmol) and dichloromethane (10 mL) were added as solvents. The reaction mixture was stirred at room temperature in the dark for 12 hours and then slowly filtered through a diatomaceous earth mat to obtain a clear filtrate. Finally, the filtrate was concentrated to 1 mL, and diethyl ether (10 mL) was added. A white precipitate immediately formed. The precipitate was collected by filtration, washed with diethyl ether (10 mL), and dried under vacuum to obtain the gold carbene complex C8. The yield was 51 mg (0.036 mmol), with a yield of 78%.

[0059] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, CDCl3): δ = 7.62 (s, 3H), 7.58 (d, J = 8.0 Hz, 6H), 7.41 (d, J = 8.0 Hz, 6H), 6.98 (s, 6H), 5.40 (s, 6H), 4.18 (t, J = 7.4 Hz, 6H),1.83 (m, 6H), 1.36 (m, 6H), 0.94 (t, J = 7.4 Hz, 9H) ppm. 13 C{ 1 ¹H NMR (100 MHz, CDCl₃): δ = 170.6, 141.6, 141.1, 134.7, 128.7,127.9, 125.2, 121.2, 120.7, 54.8, 51.4, 33.1, 19.7, 13.7 ppm. HRMS (ESI, positive ions): m / z = 1199.7145 (calcd for [c8-Au2-Cl3 + (CH3OH)9] 1+ 1199.6429). Synthesis of S203 and discrete gold(I)sulfur cluster cage d8 The synthetic chemical reaction formula is shown below:

[0060] Specifically, the following steps are included: First, the tridentate gold carbene complex C8 (35 mg, 0.025 mmol) was dissolved in a 3 mL mixture of dichloromethane, ethanol, and pyridine in a 1:1:1 volume ratio, and freshly generated H2S gas was bubbled into the solution. The reaction was stirred at room temperature for 12 hours, and the solvent was removed under vacuum to obtain a white solid. The obtained white solid was then transferred to a sample tube containing 5 mL of methanol to obtain a suspension. A saturated KOTf (28 mg, 0.15 mmol) methanol solution was slowly added to the suspension, and a large amount of white flocculent precipitate was immediately formed. The reaction was carried out at ambient temperature for 12 hours. Finally, the mixture was centrifuged, the supernatant was removed, the solid was washed with 5 mL of methanol, and dried under vacuum to obtain discrete gold(I)sulfur cluster cage D8, with a yield of 12 mg (0.002 mmol), representing a yield of 32%.

[0061] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (600 MHz, CD3CN): δ = 7.85 (d, J = 12.0 Hz, 24H), 7.20 (d, J = 2.7Hz, 12H), 6.69 (d, J = 2.7 Hz, 12H), 6.48 (d, J = 12.0 Hz, 24H), 6.22 (d, J =21.4 Hz, 12H), 6.13 (s, 12H), 5.14 (d, J = 21.5 Hz, 12H), 4.12 (m, 12H), 3.22(m, 12H), 1.61 (m, 12H), 1.50 (m, 12H), 1.24 (m, 24H), 0.89 (t, J = 12.0 Hz, 36H) ppm. 13 C{ 1 H NMR (150 MHz, CD3CN): δ= 179.0, 140.9, 140.2, 137.0, 130.3,127.4, 123.8, 122.3, 121.0, 54.7, 51.1, 33.2, 20.2, 13.9 ppm. HRMS (ESI, positive ions): m / z = 1337.8259 (calcd for [d8-4OTf] 4+ 1337.8135). Example 3: A method for preparing discrete gold(I)sulfur cluster cages based on nitrogen heterocyclic carbene protection (a schematic diagram of the construction of discrete gold(I)sulfur cluster cages is shown in Figure 1). Figure 1 (As shown), including the following steps: Synthesis of S301 and tridentate imidazole onium salt B12 The synthetic chemical reaction formula is shown below:

[0062] Specifically, the following steps are included: First, add 1,3,5-tris[4-(4-bromomethyl)phenyl]phenyl]phenyla12 (212 mg, 0.26 mmol, according to the literature J. Am. Chem. Soc. 1993, 115, 4076) to a 50 mL Schlenk reaction tube. 4086 was prepared, and 1-butylimidazole (268 mg, 2.2 mmol) was added to N,N-dimethylformamide (DMF, 5 mL) as a solvent. The resulting mixture was reacted at 120 °C for 24 hours. After cooling to room temperature, the reaction solution was concentrated to 2 mL, and ethyl acetate (20 mL) solution was added to the above reaction. A large amount of white flocculent precipitate precipitated. The solid was collected by filtration, washed with ethyl acetate (20 mL), and dried under vacuum. The resulting solid was then dissolved in 10 mL of methanol solution, and 5 mL of methanol solution containing NH4PF6 (424 mg, 2.6 mmol) was added. A white precipitate precipitated immediately. The reaction was stirred at room temperature for 12 hours. Finally, the precipitate was collected by filtration, washed with methanol (20 mL), and dried under vacuum to obtain tridentate imidazole onium salt b8, with a yield of 249 mg (0.18 mmol), a yield of 69%.

[0063] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, CD3CN): δ= 8.59 (s, 3H), 8.02 (s, 3H), 7.97 (d, J =8.0 Hz, 6H), 7.80 (m, 12H), 7.50 (d, J = 8.0 Hz, 6H), 7.43 (d, J = 1.6 Hz, 6H),5.38 (s, 6H), 4.14 (t, J = 7.3 Hz, 6H), 1.83 (m, 6H), 1.34 (m, 6H), 0.95 (t, J = 7.3 Hz, 9H) ppm. 13 C{ 1 H NMR (100 MHz, CD3CN): δ = 142.5, 141.9, 141.0, 140.1, 136.4,134.0, 130.1, 128.8, 128.5, 128.4, 125.7, 123.8, 123.4, 53.4, 50.4, 32.3,19.9, 13.6ppm. HRMS (ESI, positive ions): m / z = 545.2324 (calcd for [b12-2PF6] 2+ 545.2607). Synthesis of S302, tridentate imidazole gold carbene complex C12 The synthetic chemical reaction formula is shown below:

[0064] Specifically, the following steps are included: First, imidazolium salt B8 (51 mg, 0.037 mmol), silver oxide (24 mg, 0.074 mmol), and tetramethylammonium chloride (24 mg, 0.22 mmol) were weighed into a 25 mL round-bottom flask. Dichloromethane (5 mL) and acetonitrile (5 mL) were added as solvents. The reaction mixture was stirred at room temperature for 12 hours in the dark. After the reaction was complete, the solvent was removed. Then, Au(THT)Cl (37 mg, 0.11 mmol) and dichloromethane (10 mL) were added as solvents. The reaction mixture was stirred at room temperature in the dark for 12 hours and then slowly filtered through a diatomaceous earth mat to obtain a clear filtrate. Finally, the filtrate was concentrated to 1 mL, and diethyl ether (10 mL) was added. A white precipitate immediately formed. The precipitate was collected by filtration, washed with diethyl ether (10 mL), and dried under vacuum to obtain the gold carbene complex C12, with a yield of 49 mg (0.030 mmol), representing a yield of 78%.

[0065] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, CDCl3): δ = 7.79 (s, 3H), 7.72 (d, J = 8.0 Hz, 6H), 7.63 (d, J = 8.0 Hz, 6H), 7.60 (d, J = 8.0 Hz, 6H), 7.40 (d, J = 8.0 Hz, 6H), 6.98 (d, J = 2.0 Hz, 3H), 6.96 (d, J = 2.0 Hz, 3H), 5.39 (s, 6H), 4.19 (t, J =8.0 Hz, 6H), 1.84 (m, 6H), 1.37 (m, 6H), 0.96 (t, J = 8.0 Hz, 9H) ppm. 13 C{ 1 ¹H NMR (100 MHz, CDCl₃): δ = 170.7, 141.9, 141.0, 140.3, 139.5,134.4, 128.7, 127.9, 127.7, 127.6, 125.0, 121.2, 120.6, 54.9, 51.5, 33.5,19.8, 13.8ppm. HRMS (ESI, positive ions): m / z = 1729.4293 (calcd for [c12+CH3OH+H2O+K] 1+ 1729.3386) . Synthesis of S303 and discrete gold(I)sulfur cluster cage d12 The synthetic chemical reaction formula is shown below:

[0066] Specifically, the following steps are included: First, the tridentate gold carbene complex C12 (30 mg, 0.018 mmol) was dissolved in a 3 mL mixture of dichloromethane, ethanol, and pyridine in a 1:1:1 volume ratio, and freshly generated H2S gas was bubbled into the solution. The reaction was stirred at room temperature for 12 hours, and the solvent was removed under vacuum to obtain a white solid. The obtained white solid was transferred to a sample tube containing 5 mL of methanol to obtain a suspension. Then, a saturated NH4PF6 (12 mg, 0.072 mmol) methanol solution was slowly added to the suspension, immediately resulting in the precipitation of a large amount of white flocculent precipitate. The reaction was continued at ambient temperature for 12 hours. Finally, the mixture was centrifuged, the supernatant was removed, the solid was washed with 5 mL of methanol, and dried under vacuum to obtain discrete gold(I)sulfur cluster cage d12, with a yield of 23 mg (0.0035 mmol), representing a yield of 78%.

[0067] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (600 MHz, CD3CN): δ = 7.88 (d, J = 12 Hz, 24H), 7.23 (m, 36H,H15), 7.14 (s, 12H), 6.88 (d, J = 12.0 Hz, 24H), 6.86 (d, J = 1.8 Hz, 12H), 6.82 (d, J = 12.0 Hz, 24H), 6.08 (d, J = 12.0 Hz, 12H), 5.11 (d, J = 12.0 Hz,12H), 4.33 (m, 12H), 3.77 (m, 12H), 1.70 (m, 12H), 1.59 (m, 12H), 1.27 (m,24H), 0.89 (t, J= 6.0 Hz, 36H) ppm. 13 C{ 1 H NMR (150 MHz, CD3CN): δ = 178.3, 141.8, 141.1, 140.5, 139.3,136.6,130.5, 129.2, 128.0, 127.7, 125.0, 122.2, 120.9, 55.0, 51.4, 33.3,20.2, 13.9 ppm. HRMS (ESI, positive ions): m / z = 1566.1679 (calcd for [d12-4PF6] 4+ 1566.1581). Example 4: A method for preparing discrete gold(I)sulfur cluster cages based on nitrogen heterocyclic carbene protection (a schematic diagram of the construction of discrete gold(I)sulfur cluster cages is shown in Figure 1). Figure 1 (As shown), including the following steps: Synthesis of S401 and tridentate imidazole bismuth salt B14 The synthetic chemical reaction formula is shown below:

[0068] Specifically, the following steps are included: First, 2,4,6-tris(4'-(bromomethyl)-[1,1'-diphenyl]-4-yl)-1,3,5-triazine a14 (615 mg, 0.75 mmol) and 1-butylimidazole (268 mg, 2.2 mmol) were added to a 50 mL Schlenk reaction tube. N,N-dimethylformamide (DMF, 10 mL) was added as a solvent, and the resulting mixture was reacted at 120 °C for 24 hours. After cooling to room temperature, the reaction solution was concentrated to 2 mL, and a large amount of white flocculent precipitate was formed by adding ethyl acetate (20 mL) to the solution. The solid was collected by filtration, washed with ethyl acetate (20 mL), and dried under vacuum. Next, the obtained solid was dissolved in 20 mL of methanol solution, and a methanol solution (5 mL) containing NH4PF6 (1231 mg, 7.55 mmol) was added. A white precipitate immediately formed, and the reaction was stirred at room temperature for 12 hours. Finally, the precipitate was collected by filtration, washed with methanol (20 mL), and dried under vacuum to obtain tridentate imidazole onium salt B14, with a yield of 858 mg (0.66 mmol) and a yield of 88%.

[0069] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, CD3CN): δ = 8.76 (d, J = 8.4 Hz, 6H), 8.60 (s, 3H), 7.82 (m, 12H), 7.51 (d, J = 8.2 Hz, 6H), 7.43 (m, 6H), 5.38 (s, 6H), 4.20 (q, J = 7.3 Hz, 6H), 1.49 (t, J = 7.3 Hz, 9H) ppm. 13 C{1H} NMR (100 MHz, CD3CN): δ = 171.9, 144.7, 141.5, 136.2, 136.1,134.5, 130.3, 130.2, 128.7, 128.2, 123.5, 123.3, 53.3, 46.0, 15.2 ppm. HRMS (ESI, positive ions): m / z = 288.1435 (calcd for [b14-3PF6] 3+ 288.1495). Synthesis of S402, tridentate imidazole kilotonide complex C14 The synthetic chemical reaction formula is shown below:

[0070] Specifically, the following steps are included: First, imidazolium salt B14 (103 mg, 0.079 mmol), silver oxide (53 mg, 0.16 mmol), and tetramethylammonium chloride (53 mg, 0.48 mmol) were weighed into a 50 mL round-bottom flask. Dichloromethane (10 mL) and acetonitrile (10 mL) were added as solvents. The reaction mixture was stirred at room temperature for 12 hours in the dark. After the reaction was complete, the solvent was removed. Then, Au(THT)Cl (80 mg, 0.25 mmol) and dichloromethane (10 mL) were added as solvents. The reaction mixture was stirred at room temperature in the dark for 12 hours and then slowly filtered through a diatomaceous earth mat to obtain a clear filtrate. Finally, the filtrate was concentrated to 1 mL, and diethyl ether (10 mL) was added. A white precipitate immediately formed. The precipitate was collected by filtration, washed with diethyl ether (10 mL), and dried under vacuum to obtain the gold carbene complex C14, with a yield of 99 mg (0.064 mmol), representing a yield of 81%.

[0071] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (400 MHz, CDCl3): δ = 8.65 (d, J = 8.3 Hz, 6H), 7.61 (m, 12H), 7.42 (d, J = 8.3 Hz, 6H), 7.02 (d, J = 1.9 Hz, 3H), 6.99 (d, J = 1.9 Hz, 3H), 5.41 (s, 6H), 4.29 (q, J = 7.3 Hz, 6H), 1.51 (t, J = 7.3 Hz, 9H) ppm. 13 C{ 1 ¹H NMR (100 MHz, CDCl₃): δ = 170.8, 170.3, 143.6, 140.4, 135.2,135.0, 129.4, 128.6, 127.7, 126.9, 121.0, 120.8, 54.8, 46.8, 16.7 ppm. HRMS (ESI, positive ions): m / z = 1620. 2862 (calcd for [c14+Na+KH] 1+ 1620.1755). Synthesis of S103 and discrete gold(I)sulfur cluster cage d14 The synthetic chemical reaction formula is shown below:

[0072] Specifically, the following steps are included: First, the tridentate gold carbene complex C14 (25 mg, 0.016 mmol) was dissolved in a mixed solution of dichloromethane-ethanol-pyridine (3 mL, 1:1:1 v / v / v), and freshly generated H2S gas was bubbled into the solution. The reaction was stirred at room temperature for 12 hours, and the solvent was removed under vacuum to obtain a white solid. The obtained white solid was transferred to a sample tube containing 5 mL of methanol to obtain a suspension. Then, a saturated NH4PF6 (26 mg, 0.16 mmol) methanol solution was slowly added to the suspension, and a large amount of white flocculent precipitate was immediately formed. The reaction was carried out at ambient temperature for 12 hours. Finally, the mixture was centrifuged, the supernatant was removed, the solid was washed with 5 mL of methanol, and dried under vacuum to obtain discrete gold(I)sulfur cluster cage d14, with a yield of 24 mg (0.0037 mmol), representing a yield of 69%.

[0073] The results of NMR and mass spectrometry characterization are as follows: 1 H NMR (600 MHz, CD3CN): δ = 8.01 (d, J = 7.9 Hz, 24H), 7.85 (d, J = 8.3Hz, 24H), 7.21, (m, 36H), 7.03 (d, J = 7.9 Hz, 24H), 6.88 (d, J = 1.5 Hz, 12H), 6.09 (d, J = 13.9 Hz, 12H), 5.13 (d, J = 13.7 Hz, 12H), 4.42 (m, 12H), 3.88 (m,12H), 1.28 (t, J = 7.2 Hz, 36H) ppm. 13 C NMR (150 MHz, CD3CN): δ = 178.0, 170.8), 143.2, 140.4, 137.6,135.9, 131.2, 129.8, 127.7, 127.1, 121.7, 121.1, 54.9, 47.0, 16.1ppm. HRMS (ESI, positive ions): m / z = 1484.7819 (calcd for [d14-4PF6] 4+ 1484.7993), 2028.0405 (calcd for [d14-3PF6] 3+ 2028.0504). Experimental Example: Chemical Composition and Crystal Structure Analysis The discrete gold(I) sulfur cluster cage d14 and the tridentate gold carbene complex c14 prepared in Example 4 were subjected to... 1 H NMR spectrum, 1 Characterized by OH DOSY spectroscopy, HR-ESI mass spectrometry, and X-ray single-crystal diffraction, discrete gold(I)sulfur cluster cage d14 1 H NMR spectrum, 1 HDOSY spectroscopy and HR-ESI mass spectrometry, as well as the tridentate gold carbene complex C14 1 H NMR spectra such as Figure 2 As shown, the X-ray single-crystal diffraction characterization results are as follows: Figure 3 As shown, the crystal structure is as follows Figure 4 As shown.

[0074] The results showed that, after assembly, the discrete gold(I)sulfur cluster cage d14 1 1H NMR spectroscopy revealed that the proton signals attributable to the methylene group near the imidazole ring and the methylene group on the flexible ligand split into two sets of doublets, possibly due to the difference in chemical environment inside and outside the cavity of the discrete gold(I)sulfur cluster d14 (e.g. Figure 2 Figure b). The diffusion-ordered NMR (DOSY) results of discrete gold(I) sulfur cluster cage d14 indicate that the signals of all cages are located on a single spectral band, suggesting that discrete gold(I) sulfur cluster cage d14 is formed as a single species. Figure 2 (Figure c). Furthermore, HR-ESI mass spectrometry data (positive ion mode) of discrete gold(I) sulfur cluster cage d14 show the corresponding [d14] 4PF6] 4+ 、[d14 3PF6] 3+ The two main peaks perfectly match the calculated isotopic distribution. For example, in m / z The peak of the isotopic distribution observed at 1484.7819 corresponds perfectly to its theoretical isotopic distribution ([d14)). 4PF6] 4+ The calculated value is 1484.7993. Figure 2 (Figure d in the middle)

[0075] In the discrete gold(I)sulfur cluster cage d14 structure, four [( μ 3-S)Au3] + The cluster node occupies each vertex of the tetrahedral cage, and each NHC ligand serves as a face of the tetrahedral cage and intersects with [( μ 3-S)Au3] + Cluster node matching ( Figure 3 Figure a). The crystal structure shows [( μ 3-S)Au3] + The distance between cluster units is 20.6–22.6 Å. Figure 3 (Figure b) The dihedral angle between adjacent benzene rings in the ligand ranges from 20.8° to 36.8°. Figure 3 (Figure c). Using the VOIDOO program, the volume of the cavity of the discrete gold(I)sulfur cluster cage d14 was calculated to be approximately 181 Å. Figure 3 The middle d figure provides favorable conditions for the study of host-guest chemistry.

[0076] The cavity shape of discrete gold(I)sulfur cluster cage d14 is close to a perfect tetrahedron, thus it is suitable for host-guest interactions with other neutral guest molecules of similar shape and size. For example, tetramethylgermanium binding (…) Figure 4 By utilizing the good spatial matching between the cavity of discrete gold(I)sulfur cluster cage d14 and tetramethylgermanium molecule, the structure of the corresponding guest was determined by cultivating host-guest complex crystals, filling the gap in the structural testing of this compound under normal pressure.

[0077] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A discrete gold(I) chalcogen cluster cage based on aza carbene protection, characterized by, The structure of the discrete gold(I) chalcogen cluster cage protected by the nitrogen heterocyclic carbene is shown as any one of formula I-IV; Formula I: ; In formula I, R includes any one of C1-C3 alkyl; X includes any one of halogen group, OTf, PF6, SbF6, BF4 and ReO4; Formula II: ; In formula II, R includes any one of C1-C3 alkyl; X includes any one of halogen group, OTf, PF6, SbF6, BF4 and ReO4; Formula III: ; In formula III, R includes any one of C1-C3 alkyl; X includes any one of halogen group, OTf, PF6, SbF6, BF4 and ReO4; Formula IV: ; In formula IV, R includes any one of C1-C4 alkyl; X includes any one of halogen group, OTf, PF6, SbF6, BF4 and ReO4.

2. The process for the preparation of discrete gold(I) chalcogen cluster cages protected by a nitrogen heterocyclic carbene radical according to claim 1, characterized in that, The preparation method of the discrete gold(I) chalcogen cluster cage shown in formula I includes the following steps: S101, reacting 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine and 1-alkyl imidazole compound in a solvent to obtain a tridentate imidazolium salt; S102, reacting the tridentate imidazolium salt obtained in S101 and silver oxide in a solvent, then adding Au(THT)Cl in a solvent to continue the reaction to obtain a tridentate imidazole gold carbene complex; S103, reacting the tridentate imidazole gold carbene complex obtained in S102 and H2S in a solvent to obtain a discrete gold(I) chalcogen cluster cage with X being Cl; S104, reacting the discrete gold(I) chalcogen cluster cage with X being Cl obtained in S103 with any one of OTf, PF6, SbF6, BF4 and ReO4 salt in a solvent to obtain a discrete gold(I) chalcogen cluster cage with X being any one of OTf, PF6, SbF6, BF4 and ReO4, respectively.

3. The method for preparing discrete gold(I)-sulfur cluster cages based on nitrogen heterocyclic carbene protection according to claim 2, characterized in that, In S101, the 1-alkyl imidazole compound includes any one of 1-methyl imidazole, 1-ethyl imidazole, 1-propyl imidazole and 1-butyl imidazole; the molar ratio of 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine and 1-alkyl imidazole compound is 1:(3-9); the reaction temperature is 100-150 ℃, and the time is 20-30 h; In S102, the molar ratio of the tridentate imidazolium salt, silver oxide and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction temperature is room temperature, and the time is 10-15 h; the temperature for continuing the reaction is room temperature, and the time is 10-15 h; In S103, the reaction temperature is room temperature, and the time is 10-15 h; In S104, the molar ratio of the discrete gold(I) chalcogen cluster cage with X being Cl and any one of OTf, PF6, SbF6, BF4 and ReO4 salt is 1:(3-12); the reaction temperature is room temperature, and the time is 10-15 h.

4. The process for the preparation of discrete gold(I) chalcogen cluster cages protected by a nitrogen heterocyclic carbene radical according to claim 1, characterized in that, The preparation method of the discrete gold(I) chalcogen cluster cage shown in formula II includes the following steps: S201, reacting 1,3,5-tris(4-bromomethylphenyl)benzene and 1-alkyl imidazole compound in a solvent, then continuing the reaction with NH4PF6 in a solvent to obtain a tridentate imidazolium salt; S202, reacting the tridentate imidazolium salt obtained in S201 and silver oxide in a solvent, and then adding Au(THT)Cl in the solvent to continue the reaction to obtain a tridentate imidazole gold carbene complex; S203, reacting the tridentate imidazole gold carbene complex obtained in S202 and H2S in a solvent to obtain a discrete gold(I) sulfur cluster cage with X being Cl; S204, reacting the discrete gold(I) sulfur cluster cage with X being Cl obtained in S203 and a salt of any one of OTf, PF6, SbF6, BF4 and ReO4 in a solvent to obtain a discrete gold(I) sulfur cluster cage with X being any one of OTf, PF6, SbF6, BF4 and ReO4, respectively.

5. The method of claim 3, wherein the method is characterized by, In S201, the 1-alkyl imidazole compound includes any one of 1-methyl imidazole, 1-ethyl imidazole, 1-propyl imidazole and 1-butyl imidazole; the molar ratio of 1,3,5-tris(4-bromomethylphenyl)benzene, 1-alkyl imidazole compound and NH4PF6 is 1:(3-9):(5-15); the reaction temperature is 100-150 ℃, and the reaction time is 20-30 h; the temperature for the continued reaction is room temperature, and the time is 10-15 h; In S202, the molar ratio of the tridentate imidazolium salt, silver oxide and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction temperature is room temperature, and the reaction time is 10-15 h; the temperature for the continued reaction is room temperature, and the time is 10-15 h; In S203, the reaction temperature is room temperature, and the reaction time is 10-15 h; In S204, the molar ratio of the discrete gold(I) sulfur cluster cage with X being Cl and the salt of any one of OTf, PF6, SbF6, BF4 and ReO4 is 1:(3-12); the reaction temperature is room temperature, and the reaction time is 10-15 h.

6. The process for the preparation of discrete gold(I) chalcogen cluster cages protected by a nitrogen heterocyclic carbene ligand basis according to claim 1, characterized in, that The preparation method of the discrete gold(I) sulfur cluster cage shown in formula III includes the following steps: S301, reacting 1,3,5-tris[4-(4-[-bromomethyl)phenyl]phenyl]benzene and 1-alkyl imidazole compound in a solvent, and then continuing the reaction with NH4PF6 in the solvent to obtain a tridentate imidazolium salt; S302, reacting the tridentate imidazolium salt obtained in S301 and silver oxide in a solvent, and then adding Au(THT)Cl in the solvent to continue the reaction to obtain a tridentate imidazole gold carbene complex; S303, reacting the tridentate imidazole gold carbene complex obtained in S302 and H2S in a solvent to obtain a discrete gold(I) sulfur cluster cage with X being Cl; S304, reacting the discrete gold(I) sulfur cluster cage with X being Cl obtained in S303 and a salt of any one of OTf, PF6, SbF6, BF4 and ReO4 in a solvent to obtain a discrete gold(I) sulfur cluster cage with X being any one of OTf, PF6, SbF6, BF4 and ReO4, respectively.

7. The process for the preparation of discrete gold(I) chalcogen cluster cages protected by a nitrogen heterocyclic carbene according to claim 6, characterized in that, In the S301, the 1-alkyl imidazole compound includes any one of 1-methyl imidazole, 1-ethyl imidazole, 1-propyl imidazole and 1-butyl imidazole; the molar ratio of the 1-alkyl imidazole compound and NH4PF6 is 1:(3-9):(5-15); the reaction temperature is 100-150 ℃, and the reaction time is 20-30 h; the temperature for the continuous reaction is room temperature, and the time for the continuous reaction is 10-15 h; In the S302, the molar ratio of the tridentate imidazolium salt, silver oxide and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction temperature is room temperature, and the reaction time is 10-15 h; the temperature for the continuous reaction is room temperature, and the time for the continuous reaction is 10-15 h; In the S303, the reaction temperature is room temperature, and the reaction time is 10-15 h; In the S304, the molar ratio of the discrete gold(I) sulfur cluster cage with X being Cl and the salt of any one of OTf, PF6, SbF6, BF4 and ReO4 is 1:(3-12); the reaction temperature is room temperature, and the reaction time is 10-15 h.

8. The process for the preparation of discrete carbene-protected gold(I) chalcogen cluster cages based on azepines as claimed in claim 1, characterized in that, The preparation method of the discrete gold(I) sulfur cluster cage shown in the formula IV includes the following steps: S401, reacting 2,4,6-tris(4'-(bromomethyl)-[1,1'-biphenyl]-4-yl)-1,3,5-triazine and 1-alkyl imidazole compound in a solvent, and then continuously reacting with NH4PF6 in a solvent to obtain a tridentate imidazolium salt; S402, reacting the tridentate imidazolium salt obtained in the S401 and silver oxide in a solvent, and then continuously reacting with Au(THT)Cl in a solvent to obtain a tridentate imidazole gold carbene complex; S403, reacting the tridentate imidazole gold carbene complex obtained in the S402 and H2S in a solvent to obtain a discrete gold(I) sulfur cluster cage with X being Cl; S404, reacting the discrete gold(I) sulfur cluster cage with X being Cl obtained in the S403 and the salt of any one of OTf, PF6, SbF6, BF4 and ReO4 in a solvent to respectively obtain a discrete gold(I) sulfur cluster cage with X being any one of OTf, PF6, SbF6, BF4 and ReO4.

9. The process for the preparation of discrete gold(I) chalcogen cluster cages protected by a nitrogen heterocyclic carbene according to claim 8, characterized in that, In the S401, the 1-alkyl imidazole compound includes any one of 1-methyl imidazole, 1-ethyl imidazole, 1-propyl imidazole and 1-butyl imidazole; the molar ratio of the 1-alkyl imidazole compound and NH4PF6 is 1:(2-9):(5-15); the reaction temperature is 100-150 ℃, and the reaction time is 20-30 h; the temperature for the continuous reaction is room temperature, and the time for the continuous reaction is 10-15 h; In the S402, the molar ratio of the tridentate imidazolium salt, silver oxide and Au(THT)Cl is 1:(1.5-2.5):(2-4); the reaction temperature is room temperature, and the reaction time is 10-15 h; the temperature for the continuous reaction is room temperature, and the time for the continuous reaction is 10-15 h; In the S403, the reaction temperature is room temperature, and the time is 10-15 h; In the S404, the molar ratio of the discrete gold(I) chalcogen cluster cage with X being Cl to any one of salts of OTf, PF6, SbF6, BF4 and ReO4 is 1:(3-12); the reaction temperature is room temperature, and the time is 10-15 h.

10. A tridentate imidazolyl gold carbene complex for synthesizing the discrete nitrogen heterocyclic carbene protected gold(I) chalcogen cluster cages of claim 1, characterized in that, The chemical structural formula is shown in formula V-VIII: Formula V: ; In formula V, R includes any one of C1-C4 alkyl; Formula VI: ; In formula VI, R includes any one of C1-C4 alkyl; Formula VII: ; In formula VII, R includes any one of C1-C4 alkyl; Formula VIII: ; In formula VIII, R includes any one of C1-C4 alkyl.

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