Halogen and unsaturated functional group co-modified tin-oxygen cluster compound and preparation method thereof

Abstract

The invention discloses a halogen and unsaturated functional group co-modified tin-oxygen cluster compound and a preparation method thereof, and relates to the technical field of functional cluster materials, and the preparation method comprises the following steps: providing an alkyl chain modified organic tin source and a ligand simultaneously containing halogen and unsaturated functional groups; the method comprises the following steps: adding a main solvent and an auxiliary solvent dispersed in the main solvent into a reaction container, and uniformly mixing to prepare a tin-oxygen cluster compound reaction system; the tin-oxygen cluster compound system is heated, the heating temperature is controlled to be 40-100 DEG C, and the reaction time is 1-7 days; and stopping heating, and standing until a solid component is separated out. The preparation method of the tin-oxygen cluster compound is simple to operate and flexible and diversified in designability, and meanwhile, the tin-oxygen cluster compound is modified by halogen and unsaturated functional groups together, so that tin-oxygen cluster nano-particles with small and uniform particle size distribution can be obtained; and a simple, convenient, economic and environment-friendly novel tin-oxygen cluster compound synthesis reference is provided for the tin-oxygen cluster compound serving as an EUV photoresist material, a nonlinear optical crystal material, a catalyst and the like.

Description

Technical Field

[0001] The invention relates to the technical field of functional cluster materials, in particular to a halogen and an unsaturated functional group co-modified tin oxide cluster and a preparation method thereof. Background Art

[0002] As an important branch of metal oxoclusters, tin oxoclusters have potential application prospects in extreme ultraviolet lithography, catalysis, biomedicine, energy materials and other fields due to their unique electronic structure and chemical activity. They have become one of the hot research areas in chemistry, materials and other disciplines. Since tin atoms have empty 5d orbitals, they can accept lone pairs of electrons to form tetra-, penta-, hexa-, and heptapho-multi-coordinated organic tin complexes with rich and varied structures. Therefore, the functional modification of tin oxoclusters has also become a research hotspot.

[0003] Tin oxy clusters modified by halogens and unsaturated functional groups are a new type of crystalline material. They combine halogens that regulate the diversity of electronic structures, unsaturated functional groups with active sites, and tin oxy clusters, providing a new type of tin oxy cluster crystalline material that can be used as a reference for catalysis, lithography, biomedicine and other fields.

[0004] The introduction of halogen atoms can not only regulate the electronic structure of the overall material, such as fluorine as a strong electron-withdrawing effect can regulate the activity of tin-oxygen clusters as Lewis acid catalysts in catalytic applications; it can also affect the hydrophilicity and hydrophobicity of tin-oxygen clusters, thereby enriching their applications in catalysis, photolithography, life chemistry and other fields; in addition, in the field of photochemistry, the introduction of halogen atoms can regulate its nonlinear optical effect, and can also increase the overall absorption of extreme ultraviolet light by tin-oxygen clusters, improve its sensitivity as a photoresist material, and even resolution, line edge roughness, etc. Therefore, the introduction of halogen atoms can bring a wealth of performance regulation effects.

[0005] The introduction of unsaturated groups can not only change the solubility of compounds, but also affect the activity and selectivity of compounds in chemical reactions. In organic synthesis, the introduction of unsaturated groups allows tin oxide clusters to be used as raw materials or building blocks to construct complex molecules with specific functions. In the field of photolithography, they can be used as monomers to initiate cross-linking and used as photoresists. In the study of life chemistry, unsaturated groups may also be used as tools or probes to study the interactions and reactions of biological molecules.

[0006] Based on the above background, this patent proposes for the first time a class of tin-oxygen cluster materials modified with both halogens and unsaturated functional groups. This material combines the advantages of electronic structure regulation of halogen atoms and unsaturated groups, as well as hydrophilicity and hydrophobicity, and is suitable for use in multiple fields such as catalysis, lithography, and life sciences. Summary of the invention

[0007] The present invention provides a tin oxy cluster modified with both halogen and unsaturated functional groups and a preparation method thereof, which solves the following technical problems: 1. The limitation of the types of functional ligand modification of the tin oxy cluster; 2. The challenge of introducing multiple functional organic ligands into the same tin oxy cluster.

[0008] In order to achieve the above object, the first aspect of the present invention is to provide a method for preparing a halogen and unsaturated functional group co-modified tin oxide cluster, one of which comprises the following steps:

[0009] Providing an alkyl chain-modified organic tin source and a ligand containing both a halogen and an unsaturated functional group;

[0010] Adding a main solvent and an auxiliary solvent dispersed in the main solvent into a reaction container and mixing them evenly to prepare a tin-oxygen cluster reaction system;

[0011] Heating the tin-oxygen cluster system, controlling the heating temperature to be 40-100° C., and the reaction time to be 1-7 days;

[0012] Stop heating and let the mixture stand until solid components are precipitated.

[0013] Furthermore, in the method of the present invention, the tin source is selected from tin-containing complexes or salts, including but not limited to one of butyl stannic acid, triphenyltin chloride, dibutyltin oxide, butyltin trichloride, dihydroxybutyltin chloride, trimethyltin hydroxide, and triphenyltin hydroxide.

[0014] Further, in the method of the present invention, the ligand is selected from carboxylic acid ligands, including any one of 4-trifluoromethylcinnamic acid, trans-2,5-bis(trifluoromethyl)cinnamic acid, 4-chloro-3-fluoromethylcinnamic acid, 4-fluoro-2-trifluoromethylcinnamic acid, 3,5-bis(trifluoromethylcinnamic acid), 3-(trifluoromethyl)butenoic acid, trifluoromethylacrylic acid, 3-trifluoromethylcinnamic acid, 4,4,4-trifluorobutenoic acid, 2-trifluoromethylcinnamic acid, trans-3,5-bis(trifluoromethylcinnamic acid) among ligands containing both halogen atoms and unsaturated groups, or any two of p-fluorobenzoic acid, p-chlorobenzoic acid, p-bromobenzoic acid, p-iodobenzoic acid, trifluoroacetic acid and p-vinylbenzoic acid, 4-(allyloxy)benzoic acid, 3,3-dimethylacrylic acid, methacrylic acid, 5-norbornene-2-carboxylic acid, acrylic acid, and methacrylic acid among ligands containing halogen atoms respectively.

[0015] Furthermore, in the method of the present invention, the main solvent is selected from one or two of acetonitrile, ethanol, methanol, n-propanol, isopropanol, n-butanol, and benzyl alcohol; the auxiliary solvent is a mixed solvent of triethanolamine, an alkaline agent and water, and the alkaline agent is selected from one of triethylamine, ethylenediamine, and sodium hydroxide solution or is not added.

[0016] Furthermore, in the synthesis reaction system of the method of the present invention, the molar ratio of the tin source to the ligand is 0.5-1 mmol: 0.5-1 mmol.

[0017] The amounts of the main solvent and the auxiliary solvent dispersed in the main solvent added are: 3-8 ml and 10-100 μl.

[0018] The dosage ratio of the main solvent to the auxiliary solvent is 50:1-150:1.

[0019] Furthermore, the method of the present invention also includes the step of mixing the ligand and the tin source evenly by physical ultrasound or heating and stirring after adding the main solvent and the auxiliary solvent to the solid reaction raw material. The ultrasound duration is 10 min-50 min, and the heating and stirring temperature is 40°C-60°C for 6 h-24 h.

[0020] Furthermore, in the method of the present invention, after the solid components in the reaction mother liquor are separated out, the method further includes the steps of washing and drying the obtained solid crystal particles.

[0021] The second aspect of the present invention aims to provide a type of tin-oxygen cluster nanoparticles prepared by the method of the present invention and modified with both halogen and unsaturated functional groups. One type of the tin-oxygen cluster structure is obtained by solvent thermal method by selecting functional ligands having both halogen and unsaturated functional groups, and its molecular formula is (n-BuSn)2[N(CH2CH2O)3]2(L)2, wherein L is selected from one of the ligands in the method of the present invention; the other type of tin-oxygen cluster structure is introduced into the tin-oxygen cluster by heating, stirring, standing and volatilizing, selecting functional ligands having both halogen and unsaturated functional groups or two functional ligands having halogen and unsaturated functional groups respectively, and its molecular formula is (n-Bu2Sn)4(μ3-O)2(L1) x (L2) y , wherein when y=0, x=4 or 2; when y=1, x=2; wherein L1 and L2 are both selected from one of the ligands of the method of the present invention.

[0022] The technical effects achieved by the present invention are:

[0023] The preparation method of the tin oxycluster compound is simple to operate and has flexible and diverse designability. It is modified with halogen and unsaturated functional groups to obtain tin oxycluster nanoparticles with small and uniform particle size distribution, providing a simple, economical and environmentally friendly reference for the synthesis of a new type of tin oxycluster compound for use as EUV photoresist materials, nonlinear optical crystal materials, catalysts, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1The figure is the result of the X-ray single crystal diffractometer test on Example 1, which indicates that the tin oxide cluster molecules obtained in Example 1 have a regular microscopic crystal structure;

[0025] Figure 2 The figure is the result of the X-ray single crystal diffractometer test on Example 2, which indicates that the tin oxide cluster molecules obtained in Example 2 have a regular microscopic crystal structure;

[0026] Figure 3 The figure is the result of the X-ray single crystal diffractometer test on Example 3, which indicates that the tin oxide cluster molecules obtained in Example 3 have a regular microscopic crystal structure;

[0027] Figure 4 The figure is the result of the X-ray single crystal diffractometer test on Example 4, which indicates that the tin oxide cluster molecules obtained in Example 4 have a regular microscopic crystal structure;

[0028] Figure 5 The figure is the result of the X-ray single crystal diffractometer test on Example 5, which indicates that the tin oxide cluster molecules obtained in Example 5 have a regular microscopic crystal structure;

[0029] Figure 6 The results of X-ray single crystal diffractometer testing of Example 6 indicate that the tin oxide cluster molecules obtained in Example 6 have a regular microscopic crystal structure;

[0030] Figure 7 The results of X-ray single crystal diffractometer testing of Example 7 indicate that the tin oxide cluster molecules obtained in Example 6 have a regular microscopic crystal structure;

[0031] Figure 8 The results of X-ray powder diffractometer testing of Example 1 indicate that the tin oxide cluster molecules obtained in Example 1 have good purity and crystallinity;

[0032] Fig. 9 The results of X-ray powder diffractometer testing of Example 2 indicate that the tin oxide cluster molecules obtained in Example 1 have good purity and crystallinity;

[0033] Fig.10 The results of X-ray powder diffractometer testing of Example 3 indicate that the tin oxide cluster molecules obtained in Example 1 have good purity and crystallinity;

[0034] Fig.11 The results of X-ray powder diffractometer testing of Example 4 indicate that the tin oxide cluster molecules obtained in Example 1 have good purity and crystallinity;

[0035] Fig.12The results of X-ray powder diffractometer testing of Example 5 indicate that the tin oxide cluster molecules obtained in Example 1 have good purity and crystallinity;

[0036] Fig.13 The results of X-ray powder diffractometer testing of Example 6 indicate that the tin oxide cluster molecules obtained in Example 1 have good purity and crystallinity;

[0037] Fig.14 The results of X-ray powder diffractometer testing of Example 7 indicate that the tin oxide cluster molecules obtained in Example 1 have good purity and crystallinity;

[0038] Fig.15 This is the infrared spectrum of the tin oxide cluster crystalline product obtained in Example 1;

[0039] Fig.16 This is the infrared spectrum of the tin oxide cluster crystalline product obtained in Example 2;

[0040] Fig.17 This is the infrared spectrum of the tin oxide cluster crystalline product obtained in Example 3;

[0041] Fig.18 This is the infrared spectrum of the tin oxide cluster crystalline product obtained in Example 4;

[0042] Fig.19 This is the infrared spectrum of the tin oxide cluster crystalline product obtained in Example 5;

[0043] Fig. 20 This is the infrared spectrum of the tin oxide cluster crystalline product obtained in Example 6;

[0044] Fig.21 This is the infrared spectrum of the tin oxide cluster crystalline product obtained in Example 7; DETAILED DESCRIPTION

[0045] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0046] The preparation method of the halogen and unsaturated functional group co-modified tin oxide cluster provided by the present invention comprises the following steps:

[0047] providing an alkyl chain-modified organic tin source, and adding a ligand to a mixture of the two;

[0048] Adding a main solvent and an auxiliary solvent dispersed in the main solvent, mixing them evenly, to obtain a tin oxide cluster reaction system;

[0049] Heating the tin oxide cluster reaction system, controlling the heating temperature to be 40-100° C., and the reaction time to be 1-7 days;

[0050] Stop heating and let the mixture stand until solid components are precipitated.

[0051] In an embodiment of the present invention, the tin source is selected from one of butyl stannoic acid, n-butyl tin trichloride, triphenyl tin chloride, dibutyl tin oxide, dihydroxybutyl tin chloride, trimethyl tin hydroxide and triphenyl tin hydroxide.

[0052] In the synthetic reaction system, the molar ratio of the tin source to the ligand is 0.5-1 mmol:0.5-1 mmol. In the exploration of some preparation methods, this ratio is changed, and finally a non-crystalline white precipitate other than the target product is obtained, and the white precipitate can be washed away by ethyl acetate.

[0053] In the embodiment of the present invention, the ligand is selected from carboxylic acid ligands, including 4-trifluoromethylcinnamic acid, trans-2,5-bis(trifluoromethyl)cinnamic acid, 4-chloro-3-fluoromethylcinnamic acid, 4-fluoro-2-trifluoromethylcinnamic acid, 3,5-bis(trifluoromethylcinnamic acid), 3-(trifluoromethyl)butenoic acid, trifluoromethylacrylic acid, 3-trifluoromethylcinnamic acid, 4,4,4-trifluorobutenoic acid, 2-trifluoromethylcinnamic acid, trans-3,5-bis(trifluoromethylcinnamic acid) among ligands containing halogen atoms, or any two of trifluoroacetic acid, p-fluorobenzoic acid, p-chlorobenzoic acid, p-bromobenzoic acid, p-iodobenzoic acid, trifluoroacetic acid and p-vinylbenzoic acid, 4-(allyloxy)benzoic acid, 3,3-dimethylacrylic acid, methacrylic acid, 5-norbornene-2-carboxylic acid, acrylic acid, and methacrylic acid among ligands containing halogen atoms. After the reaction, the ligand will coordinate with the tin oxide cluster to balance the positive charge of the cluster core and play a certain stabilizing role in the formation of tin oxide cluster crystals.

[0054] In the embodiment of the present invention, the main solvent can be selected from one or two of ethanol, acetonitrile, methanol, n-propanol, isopropanol, n-butanol, and benzyl alcohol, and the auxiliary solvent is a mixed solvent of triethanolamine, an alkaline agent, and water, and the alkaline agent is selected from one of triethylamine, ethylenediamine, and sodium hydroxide solution or is not added. The role of the solvent is to assist the carboxylic acid ligand to remove protons so as to coordinate with the tin oxide cluster core. By controlling the amount of triethanolamine and ethanol, the kinetic process of the reaction can be further optimized to obtain tin oxide clusters with higher yield or purity.

[0055] In the embodiment of the present invention, the amounts of the main solvent and the auxiliary solvent dispersed in the main solvent added are: 3-8 ml and 10-100 μl.

[0056] The dosage ratio of the main solvent to the auxiliary solvent is 50:1-150:1.

[0057] In the embodiment of the present invention, after the main solvent and the auxiliary solvent are added to the solid reaction raw material, a step of uniformly mixing the ligand and the tin source by physical ultrasound or heating and stirring is also included. The duration of ultrasound is based on the uniform dispersion of the above materials and the absence of obvious large solid particles. The duration of ultrasound in the present invention is selected to be 10min-50min to achieve the purpose of the present invention.

[0058] In the embodiment of the present invention, the thermodynamic process of hydrolysis of the tin source in the reaction mother solution is realized by controlling the temperature, a nano-sized molecular cluster compound is formed, and the precipitated from the reaction system in the form of a crystal with regular morphology, and the microstructure of the tin oxide cluster nanoparticles is known by X-ray single crystal diffractometer testing. After the reaction system is stopped from heating, it is also necessary to slowly cool and stand at room temperature for 24 hours so that the reaction system gradually reaches the lowest energy state, at which time the functional ligand and the tin source will precipitate in the form of tin oxide cluster crystals, and the precipitated compound crystals have the advantages of small particle size and uniform size distribution.

[0059] In certain embodiments of the present invention, the solid components precipitated by standing still include some white impurity powders in addition to the target tin-vanadium oxygen cluster compound. In order to remove the impurity powders, after the solid components in the reaction mother liquor are precipitated, the steps of washing and drying the crystal particles are also included. The reagent for washing the solid components is a common solvent that cannot dissolve the target product but can dissolve the impurity powders, and ethyl acetate can be selected. The supernatant in the reaction system is sucked out, ethyl acetate is added, the impurities are quickly dissolved, and the pure product is obtained by filtration, and the crystals are dried at room temperature.

[0060] The above-mentioned solvent thermal method of the present invention introduces a functional ligand containing both a halogen and an unsaturated functional group, and the obtained tin oxy-cluster compound has a molecular formula of (n-BuSn)2[N(CH2CH2O)3]2(L)2, wherein L is selected from one of the above-mentioned ligands. Specifically, the tin oxy-cluster molecule includes a tin oxy-cluster central cluster core and a carboxylic acid ligand coordinated around it and containing a halogen atom and an unsaturated group, and is in a crystalline shape with regular morphology.

[0061] Furthermore, another method of the present invention is to introduce a tin-oxygen cluster compound by heating, stirring, and standing to volatilize, selecting a functional ligand having both a halogen and an unsaturated functional group or two functional ligands having a halogen and an unsaturated functional group respectively, and the molecular formula thereof is (n-Bu2Sn)4(μ3-O)2(L1) x (L2) y , wherein when y=0, x=4 or 2; when y=1, x=2; wherein L1 and L2 are both selected from one of the ligands of the method of the present invention.

[0062] In the implementation of the method of the present invention, ethanol is selected as the main solvent, and the solid reaction raw materials are added to the solvent to obtain a tin-oxygen cluster reaction system.

[0063] In an embodiment of the present invention, the reaction system is heated and stirred to uniformly mix the ligand and the tin source.

[0064] In the embodiment of the present invention, the heating and stirring are performed so as to make the entire reaction system clear. The stirring temperature of the present invention is 40°C-60°C, and the stirring time is 6h-24h, which can achieve the purpose of the present invention.

[0065] In the embodiment of the present invention, after the heating and stirring of the reaction system is stopped, it is necessary to slowly cool it at room temperature and let it stand for volatilization to make the reaction system supersaturated. At this time, the functional ligand and the tin source will precipitate in the form of tin oxide cluster crystals. The precipitated compound crystals have the advantages of small particle size and uniform size distribution.

[0066] In certain embodiments of the present invention, after the reaction mother liquor is evaporated to the point where crystals are precipitated and part of the mother liquor remains, the target product is filtered out and the crystals are dried at room temperature.

[0067] Unless otherwise specified, the raw materials used in the following examples are commercially available.

[0068] Embodiment 1:

[0069] 0.104 g of butyl stannoic acid and 0.108 g of 3-trifluoromethylcinnamic acid were mixed in a 10 mL reaction container, 5 mL of ethanol and 2 drops of triethanolamine were added in sequence, and the mixture was uniformly mixed by ultrasonication for 30 min.

[0070] After stopping the ultrasound, the reaction vessel was placed in an oven at 60° C. and the reaction was continued at this temperature for 72 h.

[0071] After the reaction is completed, the reaction vessel is taken out and slowly cooled. It is allowed to stand at room temperature for 24 hours to precipitate strip crystals. The solid product is filtered out and washed several times with ethyl acetate to obtain pure colorless and transparent strip single crystals. The solid components are allowed to dry completely at room temperature to obtain tin oxide cluster nanoparticles.

[0072] Embodiment 2:

[0073] 0.248 g of dibutyltin oxide and 0.216 g of 3-trifluoromethylcinnamic acid were mixed in a 100 mL reaction container, and 30 mL of methanol were added in sequence. The mixture was heated and stirred under reflux at 45° C. to mix evenly until the mixture was clear.

[0074] After clarification, the reaction vessel was placed at 45°C for 12 hours.

[0075] After the reaction is completed, the reaction vessel is taken out and slowly cooled, and allowed to stand for volatilization. After the reaction mother liquor evaporates until crystals are precipitated and part of the mother liquor remains, the target product is filtered out, and the crystals are dried at room temperature.

[0076] The solid component was allowed to dry completely at room temperature to obtain tin oxide cluster nanoparticles.

[0077] Embodiment 3:

[0078] 0.248 g of dibutyltin oxide and 0.140 g of 4,4,4-trifluorobutenoic acid were mixed in a 100 mL reaction container, and 30 mL of ethanol were added in sequence. The mixture was heated and stirred under reflux at 45° C. to mix evenly until the mixture was clear.

[0079] After clarification, the reaction vessel was placed at 45°C for 12 hours.

[0080] After the reaction is completed, the reaction vessel is taken out and slowly cooled, and allowed to stand for volatilization. After the reaction mother liquor evaporates until crystals are precipitated and part of the mother liquor remains, the target product is filtered out, and the crystals are dried at room temperature.

[0081] The solid component was allowed to dry completely at room temperature to obtain tin oxide cluster nanoparticles.

[0082] Embodiment 4:

[0083] 0.248 g of dibutyltin oxide, 37 μl of trifluoroacetic acid and 42 μl of methacrylic acid were mixed in a 100 mL reaction container, and 30 mL of ethanol were added in sequence. The mixture was heated and stirred under reflux at 45° C. to mix evenly until it became clear.

[0084] After clarification, the reaction vessel was placed at 45°C for 12 hours.

[0085] After the reaction is completed, the reaction vessel is taken out and slowly cooled, and allowed to stand for volatilization. After the reaction mother liquor evaporates until crystals are precipitated and part of the mother liquor remains, the target product is filtered out, and the crystals are dried at room temperature.

[0086] The solid component was allowed to dry completely at room temperature to obtain tin oxide cluster nanoparticles.

[0087] Embodiment 5:

[0088] 0.248 g of dibutyltin oxide and 0.216 g of 2-trifluoromethylcinnamic acid were mixed in a 100 mL reaction container, and 30 mL of methanol were added in sequence. The mixture was heated and stirred under reflux at 45° C. to mix evenly until the mixture was clear.

[0089] After clarification, the reaction vessel was placed at 45°C for 12 hours.

[0090] After the reaction is completed, the reaction vessel is taken out and slowly cooled, and allowed to stand for volatilization. After the reaction mother liquor evaporates until crystals are precipitated and part of the mother liquor remains, the target product is filtered out, and the crystals are dried at room temperature.

[0091] The solid component was allowed to dry completely at room temperature to obtain tin oxide cluster nanoparticles.

[0092] Embodiment 6:

[0093] 0.248 g of dibutyltin oxide and 0.216 g of 4-trifluoromethylcinnamic acid were mixed in a 100 mL reaction container, and 30 mL of methanol were added in sequence. The mixture was heated and stirred under reflux at 45° C. to mix evenly until the mixture was clear.

[0094] After clarification, the reaction vessel was placed at 45°C for 12 hours.

[0095] After the reaction is completed, the reaction vessel is taken out and slowly cooled, and allowed to stand for volatilization. After the reaction mother liquor evaporates until crystals are precipitated and part of the mother liquor remains, the target product is filtered out, and the crystals are dried at room temperature.

[0096] The solid component was allowed to dry completely at room temperature to obtain tin oxide cluster nanoparticles.

[0097] Embodiment 7:

[0098] 0.248 g of dibutyltin oxide and 0.284 g of trans-3,5-bis(trifluoromethylcinnamic acid) were mixed in a 100 mL reaction container, and 30 mL of methanol were added in sequence. The mixture was heated and stirred under reflux at 45° C. to mix evenly until it became clear.

[0099] After clarification, the reaction vessel was placed at 45°C for 12 hours.

[0100] After the reaction is completed, the reaction vessel is taken out and slowly cooled, and allowed to stand for volatilization. After the reaction mother liquor evaporates until crystals are precipitated and part of the mother liquor remains, the target product is filtered out, and the crystals are dried at room temperature.

[0101] The solid component was allowed to dry completely at room temperature to obtain tin oxide cluster nanoparticles.

[0102] The above-mentioned embodiment was tested in the following experimental examples.

[0103] Experimental Example 1: The crystal structure of the obtained tin oxide cluster was tested by X-ray single crystal diffractometer. The results can be seen in Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 , Figure 6 , Figure 7 .

[0104] Experimental Example 2: X-ray powder diffraction patterns of the tin oxide cluster crystalline products prepared in Examples 1 to 7 are as follows: Figure 8 , Fig. 9 , Fig.10 , Fig.11 , Fig.12 , Fig.13 , Fig.14 .

[0105] Experimental Example 3: Infrared spectra of the tin oxide cluster crystalline products prepared in Examples 1 to 7, as shown in FIG. Figure 8 , Fig.15 , Fig.16 , Fig.17 , Fig.18 , Fig.19 , Fig. 20 , Fig.21 .

[0106] It should be further explained that the above implementation modes are only used to further illustrate the technical solution of the present invention, and are not used to limit the protection scope of the present invention. The embodiments do not cover all the options in the technical solution of the present invention. Although the selection of all raw materials and process conditions in the technical solution is not explained one by one through examples, they can achieve the purpose of the present invention and achieve the expected technical effect. Any obvious adjustments and modifications made to the technical solution of the present invention that belong to the technical concept of the present invention should fall within the protection scope of the present invention.

Claims

1. A method for preparing a halogen- and unsaturated functional group-modified tin-oxygen cluster, characterized in that: The steps include: Providing an alkyl chain-modified organic tin source and a ligand containing both a halogen and an unsaturated functional group; Adding a main solvent and an auxiliary solvent dispersed in the main solvent into a reaction container and mixing them evenly to prepare a tin-oxygen cluster reaction system; Heating the tin-oxygen cluster system, controlling the heating temperature to be 40-100° C., and the reaction time to be 1-7 days; Stop heating and let stand until solid components are precipitated; In the synthetic reaction system, the molar ratio of the tin source to the ligand is 0.5-1 mmol: 0.5-1 mmol; The amount of the main solvent and the auxiliary solvent dispersed in the main solvent added is: 3-8 ml and 10-100 μl; The dosage ratio of the main solvent to the auxiliary solvent is 50:1-150:

1.

2. The preparation method according to claim 1, characterized in that: The tin source is selected from tin-containing complexes or salts, including but not limited to one of butyl stannic acid, triphenyl tin chloride, dibutyl tin oxide, butyl tin trichloride, dihydroxybutyl tin chloride, trimethyl tin hydroxide, and triphenyl tin hydroxide.

3. The preparation method according to claim 1, characterized in that the ligand The ligand is selected from carboxylic acid ligands, including any one of 4-trifluoromethylcinnamic acid, trans-2,5-bis(trifluoromethyl)cinnamic acid, 4-chloro-3-fluoromethylcinnamic acid, 4-fluoro-2-trifluoromethylcinnamic acid, 3,5-bis(trifluoromethylcinnamic acid), 3-(trifluoromethyl)butenoic acid, trifluoromethylacrylic acid, 3-trifluoromethylcinnamic acid, 4,4,4-trifluorobutenoic acid, 2-trifluoromethylcinnamic acid, trans-3,5-bis(trifluoromethylcinnamic acid) among the ligands containing both halogen atoms and unsaturated groups, or any two of p-fluorobenzoic acid, p-chlorobenzoic acid, p-bromobenzoic acid, p-iodobenzoic acid, trifluoroacetic acid and p-vinylbenzoic acid, 4-(allyloxy)benzoic acid, 3,3-dimethylacrylic acid, methacrylic acid, 5-norbornene-2-carboxylic acid, acrylic acid and methacrylic acid among the ligands containing halogen atoms respectively.

4. The preparation method according to claim 1, characterized in that The solvent is selected from one or two of acetonitrile, ethanol, methanol, n-propanol, isopropanol, n-butanol and benzyl alcohol; the auxiliary solvent is a mixed solvent of triethanolamine, an alkaline agent and water, and the alkaline agent is selected from one of triethylamine, ethylenediamine and sodium hydroxide solution or is not added.

5. The preparation method according to claim 1, characterized in that: The method further includes the step of uniformly mixing the ligand and the tin source by physical ultrasound or heating and stirring after adding the main solvent and the auxiliary solvent to the solid reaction raw material. The ultrasound duration is 10 min-50 min, and the heating and stirring temperature is 40° C.-60° C. for 6 h-24 h.

6. The preparation method according to claim 1, characterized in that: After the reaction system was stopped from heating, it was slowly cooled at room temperature and allowed to stand for 24 h.

7. The preparation method according to claim 1, characterized in that: After the solid components in the reaction mother liquid are separated out, the process also includes the steps of washing and drying the obtained solid crystal particles.

8. A class of tin-oxygen cluster nanoparticles prepared by the method of the present invention and modified with halogen and unsaturated functional groups at the same time, wherein the molecular formula of one class of the tin-oxygen clusters is (n-BuSn)2[N(CH2CH2O)3]2(L)2, wherein L is selected from one of the ligands of the method of the present invention, and the molecular formula of another class is (n-Bu2Sn)4(μ3-O)2(L1) x (L2) y , wherein when y=0, x=4 or 2; when y=1, x=2; wherein L1 and L2 are both selected from one of the ligands of the method of the present invention.

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