A complex consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 Nanoclusters and their preparation methods and applications

Abstract

The present invention provides a kind of alkyne ligand and Ph2PS2 ‑ Ligand-protected high-core Ag 104 Nano clusters and their preparation method and application. The nano clusters of the present invention are composed of the main ligand RC≡C ‑ and auxiliary ligand Ph2PS2 ‑ Joint protection, chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ The silver nanoclusters of the present invention have a clear composition and novel structure; the preparation steps are simple, the preparation conditions are mild, the raw materials are readily available, and the yield is large, which has the potential for industrial production. The obtained silver nanoclusters have photoluminescence properties and a long fluorescence lifetime of about 11.5μs, which is a phosphorescence phenomenon. Their fluorescence intensity increases with decreasing temperature and changes linearly, which has potential application value in optical thermometers.

Description

Technical Field

[0001] The present invention relates to a method comprising an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The invention relates to a nanocluster and a preparation method and application thereof, belonging to the technical field of nanocluster and fluorescent material. Background Art

[0002] Ag(I) nanoclusters are formed by monovalent silver ions and anions or organic ligands through covalent anionic and cationic interactions, metal-philic interactions, hydrogen bonds, and CH…π interactions. High-nuclear silver nanoclusters have attracted considerable research attention due to their beautiful structure and excellent optical, electronic, and catalytic properties. These unique properties are primarily determined by their quantum size and surface structure. Therefore, revealing the precise structure of metal nanoclusters is of great significance in fundamental research, especially for large silver nanoclusters (with >100 silver atoms). This is fundamental to understanding surface ligand arrangement, metal-metal and metal-organic ligand interactions, the relationship between performance and structure, and the mechanisms of growth and evolution.

[0003] Surface-passivating ligands significantly influence the geometry, electronic structure, and properties of silver nanoclusters. Alkyne molecules, as a novel protecting ligand, have attracted widespread interest due to their strong binding affinity to metals via π and σ bonds, unlike the widely studied thiol and phosphine ligands. Metal-carbon interactions impart diverse coordination modes to nanoclusters protected by alkyne ligands, enabling the realization of nanoclusters with novel structural, optical, and catalytic properties.

[0004] However, currently, high-nuclearity silver nanoclusters are rare and face challenges such as difficulty in crystallization, poor stability, low yield, and difficulty determining their structure. Therefore, the synthesis, crystallization, characterization, and further exploration of their practical applications remain the four primary challenges in this field. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention provides a - Ligand-protected high-core Ag 104 Nanoclusters and their preparation methods and applications. The silver nanoclusters synthesized by the present invention have clear composition and novel structure; the preparation steps are simple, the preparation conditions are mild, the raw materials are easily available, the yield is large, and they have the potential for industrial production; the obtained silver nanoclusters are composed of the main ligand RC≡C - and auxiliary ligand Ph2PS2 - Co-protected high-nuclear Ag 104Nanoclusters; the obtained silver nanoclusters have photoluminescence properties and a long fluorescence lifetime of about 11.5μs, which is a phosphorescence phenomenon; their fluorescence intensity increases with decreasing temperature and changes linearly, and has potential application value in optical thermometers.

[0006] The technical solutions of the present invention are as follows:

[0007] The present invention aims to provide a method for preparing a novel ligand-based compound comprising an alkyne ligand and a Ph2PS2 - Ligand-protected high-core Ag 104 Nanoclusters, the high-core Ag 104 Nanoclusters are composed of the main ligand RC≡C - and auxiliary ligand Ph2PS2 - Joint protection; chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ .

[0008] According to the present invention, preferably, the ligand RC≡C - In the embodiment, the substituent R is one of cyclopropyl, tert-butyl, phenyl or substituted phenyl; preferably, the substituent in the substituted phenyl is -CH3, -OCH3, -CH4 or -F. - It is obtained by losing hydrogen from RC≡CH; ligand Ph2PS2 - It is composed of the compound [(Ph2PS2 - )·(Et3NH + )] obtained, wherein Ph is benzene.

[0009] According to the present invention, preferably, PO4 3- As an anion template, it is provided by NaH2PO4, Na2HPO4, Na3PO4 or K3PO4, which plays the role of passivating silver cores, guiding the formation of silver nanoclusters, and participating in the formation of the final structure; PO4 3- Distributed in high-core Ag 104 The innermost and middle layers of the nanocluster structure.

[0010] According to the preferred embodiment of the present invention, high-nuclear Ag 104 The center of the nanocluster is a regular tetrahedron PO4 3- Template, connected to 4 Ag atoms outward, these 4 Ag atoms surround PO4 3- The template is arranged in a quadrilateral; 12 PO4 3- The templates are divided into 4 groups, each with 3 as a group, and the PO4 3- The template is composed of 4 tetrahedrons; through PO43- The O atoms interact with the Ag atoms and the Ag and Ag interact with each other, connecting the outermost Ag 100 Metal shell; 48 RC≡C - Ligand and 12 Ph2PS2 - Ligand coordination distribution on Ag 100 Around the metal shell.

[0011] According to the preferred embodiment of the present invention, the high-nuclear Ag 104 The microscopic morphology of the nanoclusters is yellow blocky crystals.

[0012] The second object of the present invention is to provide the above-mentioned alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The method for preparing nanoclusters comprises the following steps:

[0013] (1) dissolving a silver source in ammonia water to obtain a silver ammonia solution; dispersing an alkyne ligand RC≡CH in an organic solvent to obtain an alkyne solution; mixing the silver ammonia solution and the alkyne solution, stirring and reacting, and then filtering, washing, and drying to obtain an alkyne silver precursor, referred to as (RC≡CAg). n ;

[0014] (2) Ph2PCl was dissolved in toluene, sulfur powder and triethylamine were added, and the mixture was fully dispersed and mixed; then the mixture was refluxed, filtered, and the filtrate was crystallized at low temperature; finally, the compound [(Ph2PS2 - )·(Et3NH + )];

[0015] (3) silver acetylene precursor, phosphate, compound [(Ph2PS2 - )·(Et3NH + )] and silver salt are fully dispersed in a polar solvent, and a mixture of alkyne ligand and Ph2PS2 is obtained by stirring reaction or low temperature solvent thermal reaction. - Ligand-protected high-core Ag 104 Nanoclusters.

[0016] According to the preferred embodiment of the present invention, in step (1), the silver source is Ag2O, AgNO3, CF3COOAg or CF3SO3Ag.

[0017] Preferably, according to the present invention, in step (1), the mass concentration of the ammonia water is 25% to 28%; and the ratio of the molar amount of the silver source to the volume of the ammonia water is 0.2 to 0.5 mol / L.

[0018] According to the present invention, preferably, in step (1), the substituent R in the alkyne ligand RC≡CH is one of cyclopropyl, tert-butyl, phenyl or substituted phenyl; preferably, the substituent in the substituted phenyl is -CH3, -OCH3, -CH4 or -F.

[0019] According to the preferred embodiment of the present invention, in step (1), the organic solvent is acetonitrile, ethanol or methanol, or a combination of two or more thereof. The ratio of the molar amount of the alkyne ligand RC≡CH to the volume of the organic solvent is 0.5 to 1.5 mol / L.

[0020] According to the preferred embodiment of the present invention, in step (1), the molar ratio of the silver source to the alkyne ligand RC≡CH is 1:1-2.

[0021] Preferably, in step (1), the stirring reaction temperature is room temperature, the stirring reaction time is 1 to 3 hours, and the stirring reaction is carried out in the dark throughout the whole process.

[0022] According to the present invention, preferably, in step (1), washing is performed using an ethanol solvent.

[0023] According to the preferred embodiment of the present invention, in step (2), the ratio of the molar amount of Ph2PCl to the volume of toluene is 0.3 to 0.9 mol / L. Ph2PCl is diphenylphosphine chloride.

[0024] According to the preferred embodiment of the present invention, in step (2), the molar ratio of sulfur powder to Ph2PCl is (2-4):1.

[0025] According to the preferred embodiment of the present invention, in step (2), the molar ratio of triethylamine to Ph2PCl is (2-4):1.

[0026] According to the preferred embodiment of the present invention, in step (2), the reflux reaction time is 5 to 6 hours.

[0027] According to the preferred embodiment of the present invention, in step (2), the temperature of the low-temperature crystallization is (-18 to 5)°C.

[0028] According to the present invention, preferably, in step (2), washing is performed using toluene solvent.

[0029] Preferably according to the present invention, in step (3), the phosphate is NaH2PO4, Na2HPO4, Na3PO4 or K3PO4.

[0030] According to the preferred embodiment of the present invention, in step (3), the silver salt is AgBF4, CF3COOAg, CF3SO3Ag, AgN(CF3SO2)2, AgNO3, MePhSO3Ag, CH3SO3Ag, PhCOOAg or CH3COOAg. 104In the chemical formula of the nanocluster, the corresponding anion type is determined by the type of silver salt here.

[0031] According to the preferred embodiment of the present invention, in step (3), the molar ratio of the silver acetylene precursor to the silver salt is (1:3) to (3:1), and the molar ratio of the phosphate to the silver salt is 1:(2 to 5). - )·(Et3NH + )] and the molar ratio of the silver salt is 1:(1~5).

[0032] According to the preferred embodiment of the present invention, in step (3), the polar solvent is one or a combination of two or more of methanol, N,N-dimethylformamide, ethanol, n-propanol, isopropanol or n-butanol; and the volume ratio of the molar amount of the silver salt to the polar solvent is 5 to 25 mmol / L.

[0033] According to the preferred embodiment of the present invention, in step (3), the silver acetylene precursor, phosphate, compound [(Ph2PS2 - )·(Et3NH + )], silver salt and polar solvent are mixed and ultrasonicated for 5 to 15 minutes at room temperature for sufficient dispersion at an ultrasonic power of 160 to 180 W to obtain a milky white solution.

[0034] According to the preferred embodiment of the present invention, in step (3), the temperature of the low-temperature solvent thermal reaction is 60-80° C., and the reaction time is 20-40 h; after the solvent thermal reaction, the temperature is naturally lowered to room temperature.

[0035] According to the preferred embodiment of the present invention, in step (3), the stirring reaction temperature is room temperature, and the stirring reaction time is 10 to 15 hours.

[0036] According to the preferred embodiment of the present invention, in step (3), the reaction solution obtained by stirring the reaction or the low-temperature solvent thermal reaction is filtered, and the filtrate is placed in the dark to evaporate at room temperature and crystallize to obtain a compound composed of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 Nanoclusters.

[0037] The third object of the present invention is to provide the above-mentioned alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 Applications of nanoclusters in photoluminescence or optical thermometers.

[0038] The technical features and beneficial effects of the present invention are as follows:

[0039] 1. The silver nanoclusters of the present invention are RC≡C - and Ph2PS2 - Binary mixed ligand protected Ag 104Nanoclusters, chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ The composition is clear and the structure is beautiful. The internal phosphate group acts as a template for the growth of silver nanoclusters, and the external alkyne ligand plays a protective role to prevent further aggregation of silver nanoclusters. - The ligand has two adjacent S atoms and two coordination sites. They have a strong chelation effect with the silver atoms and a strong coordination ability. They can control the growth of the silver shell to a certain extent and have a shrinking effect on the size of the silver nanoparticles, preventing them from excessively aggregating into disordered silver nanoparticles. Therefore, the introduction of Ph2PS2 - Ligands can help enhance the stability of the structure. In the existing literature, there are few studies on silver nanoclusters protected by alkyne ligands with more than 100 silver cores, and even fewer with precise structures. 112 (Angew.Chem.Int.Ed.2020,59,5312–5315), Ag 120 (Chem. Commun., 2016, 52, 6119–6122), Ag 148 (Nanoscale, 2022, 14, 1971–1977) and Ag 216 (Nanoscale, 2017, 9, 8930–8937), but its synthesis steps are not as simple as those in the present invention, the atoms contained in some clusters are not clearly analyzed, and there is still a lack of exploration of the cluster properties.

[0040] 2. The synthesis steps of the silver nanoclusters of the present invention are simple, the synthesis time is short, the synthesis conditions are mild, the raw materials are easily available, the yield is high, and it has the potential for industrial production.

[0041] 3. Step (1) of the present invention: silver acetylene precursor (RC≡CAg) n During the synthesis, regardless of the silver source used, the molar ratio of the Ag salt to the alkyne (RC≡CH) is preferably 1:1-2, so as to obtain an alkyne silver precursor with high purity and high yield.

[0042] 4. The solvent used in the synthesis of silver nanoclusters in step (3) of the present invention is a polar solvent to promote the dissolution of the raw materials. The target product can be obtained by stirring at room temperature or by solvent thermal reaction. The silver salt added in step (3) of the present invention plays a role in promoting the depolymerization of the acetylene silver precursor. If the silver salt is not added, the acetylene silver precursor will mostly exist in the form of a polymer, which is not conducive to the formation of silver nanoclusters. At the same time, the added silver salt also plays a role in providing counter anions, which is conducive to the crystallization of the silver nanoclusters.

[0043] 5. High-nuclear Ag of the present invention 104 Nanoclusters have photoluminescence properties and can emit red fluorescence under 480nm laser irradiation, and have a long fluorescence lifetime of 11.5μs, which is a phosphorescence phenomenon. The fluorescence intensity increases with decreasing temperature. According to the formula Fitting calculations show that the sensitivity of the fluorescence intensity to temperature changes linearly, indicating that the silver nanoclusters of the present invention have potential application value as optical thermometers. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Front view of a schematic diagram of the overall structure of the nanocluster.

[0045] Figure 2 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Side view of a schematic diagram of the overall structure of the nanocluster.

[0046] Figure 3 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Crystalline photograph of nanoclusters.

[0047] Figure 4 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Structural analysis of nanoclusters.

[0048] Figure 5 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Structural analysis of the ligand-protected nanoclusters.

[0049] Figure 6 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Electrospray ionization mass spectra of nanoclusters.

[0050] Figure 7 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Liquid UV spectrum of nanoclusters.

[0051] Figure 8 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Solid-state UV spectrum of nanoclusters.

[0052] Figure 9 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Temperature-dependent fluorescence spectra of nanoclusters.

[0053] Figure 10 The high-nuclear Ag synthesized in Example 1 of the present invention 104 Room-temperature fluorescence lifetime diagram of nanoclusters.

[0054] Figure 11 (a) is the high-nuclear Ag synthesized in Example 1 of the present invention 104 The ratio of the fluorescence intensity of the nanoclusters at different temperatures to the fluorescence intensity at 283K was plotted against temperature and fitted into a graph; Figure 11 (b) is based on Figure 11 (a) Sensitivity of fluorescence intensity to temperature (Sr) calculated by the fitted equation. DETAILED DESCRIPTION

[0055] The present invention will be further described below with reference to specific embodiments and drawings, but is not limited thereto.

[0056] Unless otherwise specified, the raw materials used in the examples are all conventional products; the methods used are all prior art unless otherwise specified.

[0057] Example 1:

[0058] A complex consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The preparation method of nanoclusters is specifically as follows:

[0059] (1) The molar ratio of silver oxide to alkyne ligand RC≡CH is 1:2, and the ratio of the molar amount of silver oxide to the volume of ammonia water is 0.22 mol / L; ethanol is selected as the organic solvent, and the ratio of the molar amount of alkyne ligand RC≡CH to the volume of organic solvent ethanol is 1.3 mol / L;

[0060] That is, 26 mmol of Ag2O was first dissolved in 120 mL of 25% ammonia water to obtain a silver ammonia solution, and then 52 mmol of the alkyne ligand cPrC≡CH (cPr = cyclopropyl) was added to 40 mL of ethanol to obtain an alkyne solution. The two solutions were then mixed together, stirred in the dark at room temperature for 2 h, filtered, washed with ethanol, and dried to obtain an alkyne silver precursor (cPrC≡CAg). n , with a yield of 80%.

[0061] (2) The molar ratio of Ph2PCl to toluene volume is 0.45 mol / L, and the molar ratio of sulfur powder or triethylamine to Ph2PCl is 3:1.

[0062] That is, 90 mmol of Ph2PCl was added to 200 mL of dry toluene solvent, and then 270 mmol of sulfur powder and 270 mmol of triethylamine were added, the mixture was dispersed and mixed evenly, and the mixture was refluxed at 120°C for 5 hours, and then filtered. The filtrate was placed in a -18°C environment and filtered after 12 hours. The crystallized solid was washed with cold toluene and dried to obtain the compound [(Ph2PS2 - )·(Et3NH+ )], with a yield of 85%.

[0063] (3) The molar ratio of cyclopropylacetylene silver precursor (cPrC≡CAg)n to silver salt is 1:1, the molar ratio of phosphate to silver salt is 1:2.5, and the compound [(Ph2PS2 - )·(Et3NH + )] and silver salt in a molar ratio of 1:5, and methanol was selected as the polar solvent.

[0064] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n , 0.05mmol CF3SO3Ag, 0.02mmol Na3PO4 and 0.01mmol [(Ph2PS2 - )·(Et3NH + )] was mixed and dissolved in 5 mL of methanol, ultrasonicated at 160 W for 10 min at room temperature until the solution turned milky white. The solution was then placed in a reactor, reacted at 70 ° C for 30 h, and then naturally cooled to room temperature. Filtered, the filtrate was evaporated in a dark environment at room temperature, and crystallized to obtain yellow block crystals of high-nuclear Ag. 104 Nanoclusters, chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ , the corresponding anion is [CF3SO3]5 5- , with a yield of 21%.

[0065] Example 2:

[0066] A complex consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The preparation method of nanoclusters is specifically as follows:

[0067] (1) The molar ratio of silver oxide to alkyne ligand RC≡CH is 1:2, and the ratio of the molar amount of silver oxide to the volume of ammonia water is 0.22 mol / L; ethanol is selected as the organic solvent, and the ratio of the molar amount of alkyne ligand RC≡CH to the volume of organic solvent ethanol is 1.3 mol / L;

[0068] That is, 26 mmol of Ag2O was first dissolved in 120 mL of 25% ammonia water to obtain a silver ammonia solution, and then 52 mmol of the alkyne ligand cPrC≡CH (cPr = cyclopropyl) was added to 40 mL of ethanol to obtain an alkyne solution. The two solutions were then mixed together, stirred in the dark at room temperature for 2 h, filtered, washed with ethanol, and dried to obtain an alkyne silver precursor (cPrC≡CAg). n, with a yield of 80%.

[0069] (2) The molar ratio of Ph2PCl to toluene volume is 0.45 mol / L, and the molar ratio of sulfur powder or triethylamine to Ph2PCl is 3:1.

[0070] That is, 90mmoL Ph2PCl was added to 200mL dry toluene solvent, and then 270mmoL sulfur powder and 270mmoL triethylamine were added, and the mixture was fully dispersed and mixed, and the mixture was refluxed at 120℃ for 5h, and then filtered. The filtrate was placed in a -18℃ environment and filtered after 12h. The crystallized solid was washed with cold toluene and dried to obtain the compound [(Ph2PS2 - )·(Et3NH + )], with a yield of 85%.

[0071] (3) The molar ratio of cyclopropylacetylene silver precursor (cPrC≡CAg)n to silver salt is 1:1, the molar ratio of phosphate to silver salt is 1:2.5, and the compound [(Ph2PS2 - )·(Et3NH + )] and silver salt in a molar ratio of 1:5, and n-propanol was selected as the polar solvent.

[0072] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n , 0.05mmol CF3SO3Ag, 0.02mmol Na3PO4 and 0.01mmol [(Ph2PS2 - )·(Et3NH + )] was mixed and dissolved in 5 mL of n-propanol, ultrasonicated at 160 W for 10 min at room temperature until the solution turned milky white. The solution was then placed in a reactor, reacted at 70 ° C for 30 h, and then naturally cooled to room temperature. Filtered, the filtrate was evaporated in a dark environment at room temperature, and crystallized to obtain yellow block crystals of high-nuclear Ag. 104 Nanoclusters, chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ , with a yield of 13%.

[0073] Example 3:

[0074] A complex consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The preparation method of nanoclusters is specifically as follows:

[0075] (1) The molar ratio of silver oxide to alkyne ligand RC≡CH is 1:2, and the ratio of the molar amount of silver oxide to the volume of ammonia water is 0.22 mol / L; ethanol is selected as the organic solvent, and the ratio of the molar amount of alkyne ligand RC≡CH to the volume of organic solvent ethanol is 1.3 mol / L;

[0076] That is, 26 mmol of Ag2O was first dissolved in 120 mL of 25% ammonia water to obtain a silver ammonia solution, and then 52 mmol of the alkyne ligand cPrC≡CH (cPr = cyclopropyl) was added to 40 mL of ethanol to obtain an alkyne solution. The two solutions were then mixed together, stirred in the dark at room temperature for 2 h, filtered, washed with ethanol, and dried to obtain an alkyne silver precursor (cPrC≡CAg). n , with a yield of 80%.

[0077] (2) The molar ratio of Ph2PCl to toluene volume is 0.45 mol / L, and the molar ratio of sulfur powder or triethylamine to Ph2PCl is 3:1.

[0078] That is, 90mmoL Ph2PCl was added to 200mL dry toluene solvent, and then 270mmoL sulfur powder and 270mmoL triethylamine were added, and the mixture was fully dispersed and mixed, and the mixture was refluxed at 120℃ for 5h, and then filtered. The filtrate was placed in a -18℃ environment and filtered after 12h. The crystallized solid was washed with cold toluene and dried to obtain the compound [(Ph2PS2 - )·(Et3NH + )], with a yield of 85%.

[0079] (3) The molar ratio of cyclopropylacetylene silver precursor (cPrC≡CAg)n to silver salt is 1:1, the molar ratio of phosphate to silver salt is 1:2.5, and the compound [(Ph2PS2 - )·(Et3NH + )] and silver salt in a molar ratio of 1:5, and methanol was selected as the polar solvent.

[0080] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n , 0.05mmol CF3SO3Ag, 0.02mmol Na3PO4 and 0.01mmol [(Ph2PS2 - )·(Et3NH + )] was mixed and dissolved in 5 mL of methanol, ultrasonicated at 160 W for 10 min at room temperature, and the solution turned milky white. The reaction was then stirred at room temperature for 12 h. Filtered, the filtrate was evaporated in a dark environment and at room temperature, and crystallized to obtain yellow block crystals of high-nuclear Ag. 104 Nanoclusters, chemical formula is [(PO4)@Ag4@(PO4) 12Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ , with a yield of 15%.

[0081] Example 4:

[0082] A complex consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The preparation method of nanoclusters is specifically as follows:

[0083] (1) The molar ratio of silver oxide to alkyne ligand RC≡CH is 1:2, and the ratio of the molar amount of silver oxide to the volume of ammonia water is 0.22 mol / L; ethanol is selected as the organic solvent, and the ratio of the molar amount of alkyne ligand RC≡CH to the volume of organic solvent ethanol is 1.3 mol / L;

[0084] That is, 26 mmol of Ag2O was first dissolved in 120 mL of 25% ammonia water to obtain a silver ammonia solution, and then 52 mmol of the alkyne ligand cPrC≡CH (cPr = cyclopropyl) was added to 40 mL of ethanol to obtain an alkyne solution. The two solutions were then mixed together, stirred in the dark at room temperature for 2 h, filtered, washed with ethanol, and dried to obtain an alkyne silver precursor (cPrC≡CAg). n , with a yield of 80%.

[0085] (2) The molar ratio of Ph2PCl to toluene volume is 0.45 mol / L, and the molar ratio of sulfur powder or triethylamine to Ph2PCl is 3:1.

[0086] That is, 90mmoL Ph2PCl was added to 200mL dry toluene solvent, and then 270mmoL sulfur powder and 270mmoL triethylamine were added, and the mixture was fully dispersed and mixed, and the mixture was refluxed at 120℃ for 5h, and then filtered. The filtrate was placed in a -18℃ environment and filtered after 12h. The crystallized solid was washed with cold toluene and dried to obtain the compound [(Ph2PS2 - )·(Et3NH + )], with a yield of 85%.

[0087] (3) The molar ratio of cyclopropylacetylene silver precursor (cPrC≡CAg)n to silver salt is 1:1, the molar ratio of phosphate to silver salt is 1:2.5, and the compound [(Ph2PS2 - )·(Et3NH + )] and silver salt in a molar ratio of 1:5, and methanol was selected as the polar solvent.

[0088] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n, 0.05mmol CF3SO3Ag, 0.02mmol K3PO4 and 0.01mmol [(Ph2PS2 - )·(Et3NH + )] was mixed and dissolved in 5 mL of methanol, ultrasonicated at 160 W for 10 min at room temperature until the solution turned milky white. The solution was then placed in a reactor, reacted at 70 ° C for 30 h, and then naturally cooled to room temperature. Filtered, the filtrate was evaporated in a dark environment at room temperature, and crystallized to obtain yellow block crystals of high-nuclear Ag. 104 Nanoclusters, chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ , with a yield of 16%.

[0089] Example 5:

[0090] A complex consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The preparation method of nanoclusters is specifically as follows:

[0091] (1) The molar ratio of silver oxide to alkyne ligand RC≡CH is 1:2, and the ratio of the molar amount of silver oxide to the volume of ammonia water is 0.22 mol / L; ethanol is selected as the organic solvent, and the ratio of the molar amount of alkyne ligand RC≡CH to the volume of organic solvent ethanol is 1.3 mol / L;

[0092] That is, 26 mmol of Ag2O was first dissolved in 120 mL of 25% ammonia water to obtain a silver ammonia solution, and then 52 mmol of the alkyne ligand cPrC≡CH (cPr = cyclopropyl) was added to 40 mL of ethanol to obtain an alkyne solution. The two solutions were then mixed together, stirred in the dark at room temperature for 2 h, filtered, washed with ethanol, and dried to obtain an alkyne silver precursor (cPrC≡CAg). n , with a yield of 80%.

[0093] (2) The molar ratio of Ph2PCl to toluene volume is 0.45 mol / L, and the molar ratio of sulfur powder or triethylamine to Ph2PCl is 3:1.

[0094] That is, 90mmoL Ph2PCl was added to 200mL dry toluene solvent, and then 270mmoL sulfur powder and 270mmoL triethylamine were added, and the mixture was fully dispersed and mixed, and the mixture was refluxed at 120℃ for 5h, and then filtered. The filtrate was placed in a -18℃ environment and filtered after 12h. The crystallized solid was washed with cold toluene and dried to obtain the compound [(Ph2PS2 -)·(Et3NH + )], with a yield of 85%.

[0095] (3) The molar ratio of cyclopropylacetylene silver precursor (cPrC≡CAg)n to silver salt is 1:1, the molar ratio of phosphate to silver salt is 1:2.5, and the compound [(Ph2PS2 - )·(Et3NH + )] and silver salt in a molar ratio of 1:5, and methanol was selected as the polar solvent.

[0096] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n , 0.05mmol CF3SO3Ag, 0.02mmol Na2HPO4 and 0.01mmol [(Ph2PS2 - )·(Et3NH + )] was mixed and dissolved in 5 mL of methanol, ultrasonicated at 160 W for 10 min at room temperature until the solution turned milky white. The solution was then placed in a reactor, reacted at 70 ° C for 30 h, and then naturally cooled to room temperature. Filtered, the filtrate was evaporated in a dark environment at room temperature, and crystallized to obtain yellow block crystals of high-nuclear Ag. 104 Nanoclusters, chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ , with a yield of 12%.

[0097] Example 6:

[0098] A complex consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The preparation method of nanoclusters is specifically as follows:

[0099] (1) The molar ratio of silver oxide to alkyne ligand RC≡CH is 1:2, and the ratio of the molar amount of silver oxide to the volume of ammonia water is 0.22 mol / L; ethanol is selected as the organic solvent, and the ratio of the molar amount of alkyne ligand RC≡CH to the volume of organic solvent ethanol is 1.3 mol / L;

[0100] That is, 26 mmol of Ag2O was first dissolved in 120 mL of 25% ammonia water to obtain a silver ammonia solution, and then 52 mmol of the alkyne ligand cPrC≡CH (cPr = cyclopropyl) was added to 40 mL of ethanol to obtain an alkyne solution. The two solutions were then mixed together, stirred in the dark at room temperature for 2 h, filtered, washed with ethanol, and dried to obtain an alkyne silver precursor (cPrC≡CAg). n , with a yield of 80%.

[0101] (2) The molar ratio of Ph2PCl to toluene volume is 0.45 mol / L, and the molar ratio of sulfur powder or triethylamine to Ph2PCl is 3:1.

[0102] That is, 90mmoL Ph2PCl was added to 200mL dry toluene solvent, and then 270mmoL sulfur powder and 270mmoL triethylamine were added, and the mixture was fully dispersed and mixed, and the mixture was refluxed at 120℃ for 5h, and then filtered. The filtrate was placed in a -18℃ environment and filtered after 12h. The crystallized solid was washed with cold toluene and dried to obtain the compound [(Ph2PS2 - )·(Et3NH + )], with a yield of 85%.

[0103] (3) The molar ratio of cyclopropylacetylene silver precursor (cPrC≡CAg)n to silver salt is 1:1, the molar ratio of phosphate to silver salt is 1:2.5, and the compound [(Ph2PS2 - )·(Et3NH + )] and silver salt in a molar ratio of 1:5, and methanol was selected as the polar solvent.

[0104] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n , 0.05mmol AgN(CF3SO2)2, 0.02mmol Na3PO4 and 0.01mmol[(Ph2PS2 - )·(Et3NH + )] was mixed and dissolved in 5 mL of methanol, ultrasonicated at 160 W for 10 min at room temperature until the solution turned milky white. The solution was then placed in a reactor, reacted at 70 ° C for 30 h, and then naturally cooled to room temperature. Filtered, the filtrate was evaporated in a dark environment at room temperature, and crystallized to obtain yellow block crystals of high-nuclear Ag. 104 Nanoclusters, chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ , with a yield of 13%.

[0105] Comparative Example 1:

[0106] The preparation method of the acetylene silver precursor is specifically as follows:

[0107] The molar ratio of silver oxide to alkyne ligand RC≡CH was changed to 1:4, and the other steps and conditions were the same as in Example 1;

[0108] That is, 13 mmol of Ag2O was first dissolved in 120 mL of 25% ammonia water, and then 52 mmol of the alkyne ligand cPrC≡CH (cPr = cyclopropyl) was added to 40 mL of ethanol. The two solutions were then mixed and stirred. A solid was quickly generated and quickly agglomerated, and no large amount of powder was formed. The preparation of the cyclopropyl silver acetylene precursor failed.

[0109] Comparative Example 2:

[0110] A method for preparing silver nanoclusters, specifically comprising:

[0111] (1) Silver acetylene precursor (cPrC≡CAg) n The preparation is the same as in Example 1;

[0112] (2) Compound [(Ph2PS2 - )@(Et3NH + )] was prepared as in Example 1;

[0113] (3) In this step, phosphate is replaced by vanadate, the molar ratio of cyclopropyl acetylene silver precursor (cPrC≡CAg)n to silver salt is 1:1, the molar ratio of vanadate to silver salt is 1:2.5, and the compound [(Ph2PS2 - )@(Et3NH + )] and silver salt in a molar ratio of 1:5, and methanol was selected as the polar solvent.

[0114] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n , 0.05mmol CF3SO3Ag, 0.02mmol Na3VO4 and 0.01mmol [(Ph2PS2 - )@(Et3NH + )] were mixed and dissolved in 5 mL of methanol and sonicated at room temperature for 10 minutes at 160 W. The solution was then placed in a reactor and reacted at 70°C for 30 hours, after which the temperature was naturally cooled to room temperature. Filtering was done, and the filtrate evaporated in the dark at room temperature, but no target product was obtained.

[0115] Comparative Example 3:

[0116] A method for preparing silver nanoclusters, specifically comprising:

[0117] (1) Silver acetylene precursor (cPrC≡CAg) n The preparation is the same as in Example 1;

[0118] (2) Compound [(Ph2PS2 - )·(Et3NH + )] was prepared as in Example 1;

[0119] (3) No silver salt is added in this step, and methanol is selected as the polar solvent.

[0120] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg) n , 0.02mmol Na3PO4 and 0.01mmol[(Ph2PS2 - )·(Et3NH + )] were mixed and dissolved in 5 mL of methanol and sonicated at room temperature for 10 minutes at 160 W. The solution was then placed in a reactor and reacted at 70°C for 30 hours, after which the temperature was naturally cooled to room temperature. The filtrate was filtered, and evaporated in the dark at room temperature, resulting in no target product.

[0121] Comparative Example 4:

[0122] A method for preparing silver nanoclusters, specifically comprising:

[0123] (1) Compound [(Ph2PS2 - )·(Et3NH + )] was prepared as in Example 1;

[0124] (2) No silver acetylene precursor is added and methanol is selected as the polar solvent.

[0125] That is, 0.05mmol CF3SO3Ag, 0.02mmol Na3PO4 and 0.01mmol [(Ph2PS2 - )·(Et3NH + )] were mixed and dissolved in 5 mL of methanol. Ultrasonication was performed at room temperature at 160 W for 10 minutes, until the solution turned milky white. This solution was then added to a reactor and reacted at 70°C for 30 hours, after which the temperature was naturally cooled to room temperature. Filtering was done, and the filtrate evaporated in the dark at room temperature, but no target product was obtained.

[0126] Comparative Example 5:

[0127] A method for preparing silver nanoclusters, specifically comprising:

[0128] (1) Silver acetylene precursor (cPrC≡CAg) n The preparation is the same as in Example 1;

[0129] (2) Compound [(Ph2PS2 - )·(Et3NH + )] was prepared as in Example 1;

[0130] (3) The solvent thermal reaction temperature in this step is 90°C, and methanol is selected as the polar solvent.

[0131] That is, 0.05mmol of cyclopropyl silver precursor (cPrC≡CAg)n , 0.05mmol CF3SO3Ag, 0.02mmol Na3PO4 and 0.01mmol [(Ph2PS2 - )·(Et3NH + )] were mixed and dissolved in 5 mL of methanol and sonicated at room temperature for 10 minutes at 160 W. The solution was then placed in a reactor and reacted at 100°C for 30 hours, after which the temperature was naturally cooled to room temperature. The filtrate was filtered, and evaporated in the dark at room temperature, resulting in no target product.

[0132] From the above comparison, it can be seen that no crystals were obtained when phosphate was replaced with vanadate, which shows that PO4 3- The uniqueness of participating in the assembly and formation of Ag104. If silver salt is not added, the acetylene silver precursor is difficult to depolymerize, and the system lacks counter anions, making it difficult to crystallize. This shows that the addition of silver salt plays an important role in the reaction. If the acetylene silver precursor is not added, the alkyne ligand cannot be provided and the product cannot be obtained, proving that the acetylene silver precursor is necessary. In addition, the solvent thermal reaction temperature cannot be too high, otherwise it will destroy the framework of the silver nanoclusters and the target product cannot be crystallized.

[0133] Experimental Example 1: Structural Characterization

[0134] The high-nuclear Ag synthesized in Example 1 104 The nanoclusters were characterized by X-ray single crystal diffraction test. The specific structure obtained by analysis can be found in Figure 1-4 .

[0135] Based on structural analysis, Ag 104 Nanoclusters have the following characteristics: (1) Complex crystal structure, consisting of 104 silver atoms, 13 PO4 3- , 48 RC≡C - Ligand and 12 Ph2PS2 - Ligand composition; (2) Ag 104 The phosphorus atom at the center of the structure is traversed by a quartic axis. Figure 2 It can be seen that its side view shape resembles a butterfly.

[0136] from Figure 3 It can be seen that the silver nanoclusters synthesized and prepared by the present invention are light yellow block crystals.

[0137] Figure 4 The structure of silver nanoclusters was further analyzed. 104 The structure is divided into 4 layers from the inside to the outside. Its center is a regular tetrahedron PO4 3- The template is connected to 4 Ag atoms, which surround PO4 3- The templates are arranged in a quadrilateral. The third layer is 12 PO43- Templates can be divided into 4 groups, each with 3 as a group, and the PO4 3- The template is composed of 4 tetrahedrons ( Figure 4 a) 12 PO4 3- According to their coordination mode, they can be divided into two types: 8 μ 11 -κ 2 :κ 3 :κ 3 :κ 3 and 4 μ 12 -κ 2 :κ 3 :κ 3 :κ 4 The first three layers of the structure can be formed using the group [(PO4)@Ag4(PO4) 12 ] indicates. Through PO4 3- The O atoms interact with the Ag atoms and the Ag...Ag interacts to connect the outermost Ag 100 Metal shell. The Ag…Ag interaction of the silver shell is mainly composed of 126 silver triangles and 4 distorted silver pentagons ( Figure 4 b). You can use Ag 100 The shell is split into front and back Ag 20 Unit and surrounding 4 Ag 16 The two Ag 20 Each unit is composed of 24 silver triangles, similar to an ellipse, with positions at 90 degrees relative to each other ( Figure 4 c) The macrocycle is composed of one of the Ag 16 After the unit is inverted by the symmetric operation center, the 4 Ag 16 The units Ag1 and Ag2 overlap with each other, and the overall shape looks like a four-petal flower ( Figure 4 d,e).

[0138] The cluster is RC≡C - and Ph2PS2 - These two ligands protect: 48 RC≡C - The ligand exhibits four different coordination modes: 16 μ3-η 1 :η 1 :η 1 , 24 μ4-η 1 :η 1 :η 1 :η 1 , 4 μ4-η 1 :η 1 :η 1 :η 2 and 4 μ2-η 1 :η1 , 12 Ph2PS2 - The ligands are all μ4-η 2 :η 2 The pattern coordination distribution around ( Figure 5 a,b,c).

[0139] Figure 6 For the high-nuclear Ag 104 Mass spectrum of the nanocluster. Positive ion ESI-MS shows two groups of signals, corresponding to +6 and +5 species in the range of m / z = 2900-3800. There is a group of broad peaks with +6 valence in the range of m / z = 2900-3200, indicating the superposition of many similar species. The main species 1a is [Ag 104 (PO4) 13 (RC≡C) 48 (C 12 H 10 PS2) 11 (CH3OH)3H2O] 6+ There is a group of +5 valence broad peaks in the range of m / z=3500-3800, and the main species 1b is [Ag 104 (PO4) 13 (RC≡C) 51 (C 12 H 10 PS2)9(CH3OH)3] 5+ .

[0140] It can be seen from this that the solution of the silver nanoclusters is basically stable under the mass spectrometry conditions. 104 Dissociate 1 Ph2PS2 - The ligand forms 1a species, but still maintains the silver skeleton and RC≡C - Ligand integrity, species 1b involves the exchange of two ligands on the surface.

[0141] Test Example 2: Performance Measurement

[0142] (1) The high-nuclear Ag synthesized in Example 1 104 Nanoclusters were tested for UV spectra of solutions and solids, such as Figure 7 , as shown in 8.

[0143] pass Figure 7 It can be seen that silver nanoclusters dissolved in dichloromethane (1 mg / mL) have an absorption band at 425 nm. Figure 8 Silver nanocluster crystals exhibit broad absorption across the ultraviolet and visible regions, centered around 380 nm. The low-energy broad absorption band can be attributed to charge transfer from the ligand to the metal, while the high-energy absorption peak is attributed to the ligand's absorption.

[0144] (2) High-nuclear Ag synthesized in Example 1 104 Study on the Photoluminescence Properties of Nanoclusters

[0145] The silver nanoclusters in the present invention can emit red fluorescence under 480nm laser irradiation. When the temperature drops from 283K to 83K, the fluorescence intensity continues to increase, and the peak position undergoes a blue shift of about 18nm ( Figure 9 ). And it has a long fluorescence lifetime of 11.5μs at room temperature ( Figure 10 ), which belongs to the phosphorescence phenomenon. According to the formula Fitting calculation shows that the sensitivity of fluorescence intensity to temperature changes linearly ( Figure 11 ). This indicates that Ag 104 Nanoclusters have the potential to be used as optical thermometer materials.

[0146] In summary, the high-nuclear Ag protected by alkyne ligands synthesized by the present invention 104 The nanoclusters not only have precise and beautiful structures, but also have excellent photoluminescence properties, and have potential application value in optical thermometers; and the synthesis method disclosed and protected by the present invention has the advantages of simple operation, mild conditions, easy availability of raw materials, large output, and ease of industrial production.

[0147] The embodiments described above are only preferred embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, any equivalent replacement, improvement, recombination, etc. made without creative work shall fall within the scope of protection of the present invention.

Claims

1. A method consisting of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 Nanoclusters, characterized in that The high-nuclear Ag 104 Nanoclusters are composed of the main ligand RC≡C - and auxiliary ligand Ph2PS2 - Joint protection; chemical formula is [(PO4)@Ag4@(PO4) 12 Ag 100 (RC≡C) 48 (Ph2PS2) 12 ] 5+ ; ligand RC≡C - In the case of a cyclopropyl group, the substituent R is a cyclopropyl group; 104 The center of the nanocluster is a regular tetrahedron PO4 3- Template, connected to 4 Ag atoms outward, these 4 Ag atoms surround PO4 3- The template is arranged in a quadrilateral; 12 PO4 3- The templates are divided into 4 groups, each with 3 as a group, and the PO4 3- The template is composed of 4 tetrahedrons; through PO4 3- The O atoms interact with the Ag atoms and the Ag and Ag interact with each other, connecting the outermost Ag 100 Metal shell; 48 RC≡C - Ligand and 12 Ph2PS2 - Ligand coordination distribution on Ag 100 Around the metal shell.

2. according to claim 1 by alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 Nanoclusters, characterized in that The high-nuclear Ag 104 The microscopic morphology of the nanoclusters is yellow blocky crystals.

3. The method according to any one of claims 1 to 2, wherein the alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The method for preparing nanoclusters comprises the steps of: (1) dissolving a silver source in ammonia water to obtain a silver ammonia solution; The alkyne ligand RC≡CH is dispersed in an organic solvent to obtain an alkyne solution; Mix the silver ammonia solution and the alkyne solution, stir and react, then filter, wash and dry to obtain the alkyne silver precursor, referred to as (RC≡CAg) n The molar ratio of the silver source to the alkyne ligand RC≡CH is 1:1~2; (2) Ph2PCl was dissolved in toluene, sulfur powder and triethylamine were added, and the mixture was fully dispersed and mixed; then the mixture was refluxed, filtered, and the filtrate was crystallized at low temperature; finally, the compound [(Ph2PS2 - )·(Et3NH + )]; the molar ratio of sulfur powder to Ph2PCl is (2-4):1; the molar ratio of triethylamine to Ph2PCl is (2-4):1; (3) silver acetylene precursor, phosphate, compound [(Ph2PS2 - )·(Et3NH + )] and silver salt are fully dispersed in a polar solvent, and a mixture of alkyne ligand and Ph2PS2 is obtained by stirring reaction or low temperature solvent thermal reaction. - Ligand-protected high-core Ag 104 Nanoclusters; the molar ratio of silver acetylene precursor to silver salt is (1:3)~(3:1), and the molar ratio of phosphate to silver salt is 1:(2~5); compound [(Ph2PS2 - )·(Et3NH + The molar ratio of the silver salt is 1:(1~5); the temperature of the low temperature solvent thermal reaction is 60-80 o C, reaction time is 20~40 h.

4. The method according to claim 3 comprising an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The method for preparing nanoclusters is characterized in that: In step (1), one or more of the following conditions are included: i. Silver source is Ag2O, AgNO3, CF3COOAg or CF3SO3Ag; ii. The mass concentration of ammonia water is 25% to 28%; the molar amount of the silver source and the volume ratio of ammonia water is 0.2 to 0.5 mol / L; iii. The organic solvent is one or a combination of two or more of acetonitrile, ethanol, or methanol; the ratio of the molar amount of the alkyne ligand RC≡CH to the volume of the organic solvent is 0.5 to 1.5 mol / L; iv. The stirring reaction temperature is room temperature, the stirring reaction time is 1-3 hours, and the stirring reaction is protected from light throughout the whole process.

5. The method according to claim 3 comprising an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The method for preparing nanoclusters is characterized in that: In step (2), one or more of the following conditions are included: i. The ratio of the molar amount of Ph2PCl to the volume of toluene is 0.3~0.9mol / L; ii. Reflux reaction time is 5~6 h; iii. The temperature of low temperature crystallization is (-18~5) o C.

6. The method according to claim 3 comprising an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The method for preparing nanoclusters is characterized in that: In step (3), one or more of the following conditions are included: i. Phosphate is NaH2PO4, Na2HPO4, Na3PO4 or K3PO4; ii. The silver salt is AgBF4, CF3COOAg, CF3SO3Ag, AgN(CF3SO2)2, AgNO3, MePhSO3Ag, CH3SO3Ag, PhCOOAg or CH3COOAg; iii. The polar solvent is methanol, N , N - one or a combination of two or more of dimethylformamide, ethanol, n-propanol, isopropanol, or n-butanol; the molar ratio of the silver salt to the volume ratio of the polar solvent is 5 to 25 mmol / L; iv. Silver acetylide precursor, phosphate, compound [(Ph2PS2 - )·(Et3NH + )], silver salt and polar solvent were mixed and then ultrasonicated for 5-15 min at room temperature for sufficient dispersion at an ultrasonic power of 160-180 W to obtain a milky white solution.

7. The method according to claim 3 comprising an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 The method for preparing nanoclusters is characterized in that: In step (3), one or more of the following conditions are included: i. After the solvent thermal reaction, the temperature is naturally cooled to room temperature; ii. The stirring reaction temperature is room temperature and the stirring reaction time is 10-15h; iii. The reaction solution obtained by stirring the reaction or low-temperature solvent thermal reaction is filtered, and the filtrate is placed in the dark to evaporate at room temperature and crystallize to obtain a compound composed of an alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 Nanoclusters.

8. The method according to any one of claims 1 to 2, wherein the alkyne ligand and Ph2PS2 - Ligand-protected high-core Ag 104 Applications of nanoclusters in photoluminescence or optical thermometers.

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