A super-large silver thiolate cluster material with silver triangle as core and a preparation method thereof

Abstract

A kind of super-large mercaptan silver cluster material with silver triangle as core and its preparation method belong to the technical field of inorganic nanomaterials, the chemical formula of the silver cluster material is: C 114 Ag 104 S 34 O2, belongs to triclinic system, space group is P-1, cell parameter is α=108.5020 (10) °, β=119.4730 (10) °, γ=96.1580 (10) °, the silver cluster material has luminescent property.

Description

Technical Field

[0001] This invention belongs to the technical field of inorganic nanomaterials, and particularly relates to an ultra-large silver thiol cluster material constructed with a silver triangle as the core and its preparation method. Background Technology

[0002] In recent years, ligand-protected, atomically precise silver and gold nanoclusters have exhibited a wide range of optical, photophysical, electronic, and chemical properties. These unique properties differ from their overall properties and are primarily characterized by quantum size and surface structure. Therefore, numerous chemists have been pursuing the design and synthesis of highly nucleated metal clusters with specialized structures.

[0003] In the preparation of high-nucleation silver thiols, various protective ligands are crucial for covering the surface of the target cluster to overcome aggregation and stabilize the cluster. It is well known that protective ligands, as the outermost surface structure, have a significant impact on the size, structure, and properties of the entire high-nucleation silver cluster.

[0004] A systematic study and in-depth understanding of the crystallization methods and assembly strategies of high-nucleothiol silver clusters is crucial for comprehending their structural-functional relationship. Therefore, there is an urgent need to explore novel ligands with multi-site and multidentate coordination modes to construct stable high-nucleothiol silver clusters. Summary of the Invention

[0005] In view of this, the present invention provides a super-large silver thiol cluster material constructed with a silver triangle as its core and a method for preparing the same, consisting of [AgS] t Bu] n Synthesized with CF3COOAg, this silver cluster material possesses luminescent properties and can be used as a luminescent material.

[0006] The present invention adopts the following technical solution:

[0007] A super-large silver thiol cluster material constructed with a silver triangle as its core, the silver cluster material being composed of [AgS] t Bu] n Synthesized with CF3COOAg, its chemical formula is: C 114 Ag 104 S 34 O2.

[0008] Furthermore, the silver cluster material belongs to the triclinic crystal system, with space group P-1 and cell parameters a=20.7869(8) Å, b=20.9235(8) Å, c=21.1028(9) Å, α=108.5020(10)°, β=119.4730(10)°. γ =96.1580(10)°,V=7181.5(5) Å 3 .

[0009] A method for preparing a super-large silver thiol cluster material with a silver triangle as its core, wherein the specific method for preparing the silver cluster material is as follows:

[0010] Step 1: Add [AgS] t Bu] n CF3COOAg is dissolved in a solvent and subjected to a solvothermal reaction to obtain a dark red suspension;

[0011] Step 2: After filtering the dark red suspension, a dark red transparent solution is obtained. The dark red transparent solution is then evaporated until dark red blocky crystals are obtained.

[0012] Furthermore, the [AgS] t Bu] n The molar ratio of CF3COOAg to CF3COOAg is 2.5:1.0.

[0013] Furthermore, the solvent is a mixed solution of isopropanol, dichloromethane, and N,N-dimethylformamide in a volume ratio of 1:1:1.

[0014] Furthermore, the pH value of the dark red suspension is 6.0.

[0015] Furthermore, the evaporation temperature of the deep red transparent solution is room temperature.

[0016] Furthermore, the solvothermal reaction temperature is 65 °C, and the reaction time is 2880 minutes.

[0017] Furthermore, the silver cluster material has luminescent properties.

[0018] The advantages and effects of this invention are as follows:

[0019] This invention relates to a super-large silver thiol cluster material constructed with a silver triangle as its core. It is an example of a high-nucleus silver cluster synthesized using tert-butylthiol ligands, and has luminescent properties, making it suitable for use in the field of luminescence. Attached Figure Description

[0020] Figure 1 This is a crystal structure diagram of the ultra-large silver thiol cluster material with luminescent properties constructed with a silver triangle as the core, as described in this invention.

[0021] Figure 2 The experimental and simulated powder diffraction curves of the ultra-large silver thiol cluster material with luminescent properties constructed with a silver triangle as the core, as presented in this invention;

[0022] Figure 3 The infrared spectrum of the ultra-large silver thiol cluster material with a silver triangle core, which has luminescent properties according to the present invention, is shown below.

[0023] Figure 4 The solid-state luminescence spectrum of the ultra-large silver thiolate cluster material with a silver triangle core, which has luminescent properties according to the present invention, is shown in the figure. The excitation wavelength is 244 nm (room temperature) and the emission wavelength is 395 nm. Detailed Implementation

[0024] The present invention will be further explained below with reference to embodiments, but these are not intended to limit the scope of protection of the present invention.

[0025] This embodiment provides a super-large silver thiol cluster material with luminescent properties, constructed with a silver triangle as its core. The chemical formula of this silver cluster material is C0. 114 Ag 104 S 34 O2 belongs to the triclinic crystal system, space group P-1, and its unit cell parameters are a=20.7869(8) Å, b=20.9235(8) Å, c=21.1028(9) Å, α=108.5020(10)°, β=119.4730(10)°. γ =96.1580(10)°,V=7181.5(5) Å 3 .

[0026] The preparation method of the aforementioned ultra-large silver thiolate cluster material with luminescent properties and constructed with a silver triangle as its core is as follows:

[0027] [AgS] t Bu] n CF3COOAg is dissolved in a mixed solution of isopropanol, dichloromethane, and N,N-dimethylformamide, and subjected to a solvothermal reaction to obtain a deep red solution, in which... t Bu refers to tert-butyl alcohol;

[0028] After filtering the dark red suspension, the dark red transparent solution was evaporated until dark red blocky crystals were obtained.

[0029] Among them, [AgS t Bu] n The molar ratio of CF3COOAg to CF3COOAg is 2.5:1.0, and the volume ratio of isopropanol, dichloromethane, and N,N-dimethylformamide in the mixed solution is 1:1:1. For silver cluster materials, the key lies in the ratio of the reactants. During the research and development process, the inventors discovered through numerous experiments that only by following the above ratio can the desired properties be synthesized. Figure 1 The silver cluster material with the crystal structure shown.

[0030] Preferably, the yellow suspension has a pH of 6.0, where a slightly acidic environment is less likely to cause the silver mirror reaction and is more conducive to the growth of Ag. +The aggregates and forms nuclei. The volatilization temperature of the above-mentioned dark red solution is room temperature, which is usually 25 °C.

[0031] The luminescence spectrum of the silver cluster material with luminescent properties in the above-described embodiments was studied. At room temperature, with an excitation wavelength of 244 nm, the largest emission peak was observed at 395 nm. Figure 4 ).

[0032] Example 1: Synthesis of a super-large silver thiol cluster material constructed with a silver triangle as the core.

[0033] [AgS] t Bu] n (0.0653 g, 0.3314 mmol) and CF3COOAg (0.0297 g, 0.1345 mmol) were dissolved in a mixed solution of isopropanol, dichloromethane and N,N-dimethylformamide in a volume ratio of 1:1:1. The solution was then placed in a reaction vessel and subjected to a reaction at 65 °C for 2880 minutes. The resulting mixed solution was a deep red solution (pH 6.0).

[0034] After filtration, the deep red solution yields a deep red transparent solution. This solution is then stored in a beaker and allowed to slowly evaporate at room temperature. After about a week, the evaporation process yields deep red blocky crystals, which are the ultra-large silver thiol clusters constructed with silver triangles as their core.

[0035] Luminescent properties of ultra-large silver thiol clusters constructed with silver triangles as their core

[0036] The silver cluster material sample prepared in Example 1 was used to study its solid-state emission spectrum at room temperature (e.g., Figure 4 As shown in the figure, at an excitation wavelength of 244 nm, the compound exhibits the largest emission peak at a wavelength of 395 nm.

[0037] Physical property testing of synthetic luminescent ultra-large silver thiolate clusters constructed with silver triangles as their core.

[0038] The luminescent silver cluster material prepared in Example 1 was further characterized as follows:

[0039] Crystal structure determination

[0040] X-ray single-crystal diffraction data of this silver thiol cluster material were collected and determined using appropriately sized single-crystal samples on a Bruker D8QUEST diffractometer. A graphite monochromator was used, with Mo-Kα (λ = 0.071073 nm) as the light source, and data reconstruction was performed using the Saint software package. SHELXL-2014The program parses the structure using the full-matrix least-squares refinement method. F 2 Structural refinement was carried out.

[0041] Detailed crystal measurement data are shown in Table 1, important bond lengths in Table 2, important bond angles in Table 3, and crystal structure diagrams are shown in Table 4. Figure 1 Powder diffraction curves are shown below. Figure 2 Infrared spectrum Figure 3 The emission spectrum is shown in Figure 4 .

[0042] Table 1: Main crystallographic data of the ultra-large silver thiol cluster material constructed with silver triangles as the core

[0043] Chemical formula <![CDATA[C 114 AG 104 S 34 O2]]> relative molecular mass 13720 Crystal system Three obliques Space Group P-1 Temperature (K) 273 (Å) 20.7869(8) (Å) 20.9235(8) (Å) 21.1028(9) (°) 108.5020(10) (°) 119.4730(10) (°) 96.1580(10) <![CDATA[V (Å 3 )]]> 7181.5(5) Z 1 <![CDATA[D / g cm -3 ]]> 3.155 <![CDATA[ μ / mm -1 ]]> 7.148 (000) 6100 Crystal size (mm) 0.250 x 0.230 x 0.230 The range of θ (°) for data collection 1.083-25.062 Limit Indicators -24<=h<=24, -24<=k<=24, -25<=l<=25 Reflection Collection 91497 Number of parameters 25377 Radiation intelligence 91497 / 25377 [R(int) = 0.0522] <![CDATA[ R 1 a [ I >2σ( I )]]]> 99.7% <![CDATA[ wR 2 b (all data)]]> <![CDATA[ F 2 Full matrix least squares method Goodness of fit 25377 / 126 / 1242 Number of reflections 3.164 Number of parameters <![CDATA[ R 1 = 0.3006, wR 2 = 0.6619]]> Number of restraint devices <![CDATA[ R 1 = 0.3711, wR 2 = 0.7022]]> Extinction coefficient n / a Maximum difference peak and pore <![CDATA[19.981-8.672e.A -3 ]]>

[0044] α R 1 = Σ||F o |–|F c || / Σ|F o |; b wR 2 = {Σ[w(F o 2 –F c 2 ) 2 ] / Σ[w(F o 2 ) 2 ]} 1 / 2

[0045] Table 2: Important bond lengths (Å)

[0046] Ag(1)-Ag(29) 2.535(9) Ag(20)-Ag(23) 2.893(14) Ag(1)-Ag(33) 2.550(9) Ag(20)-Ag(43) 3.01(3) Ag(1)-Ag(45) 2.572(8) Ag(20)-Ag(39) 3.051(10) Ag(1)-Ag(6) 2.920(5) Ag(20)-Ag(50) 3.033(16) Ag(1)-Ag(3) 2.958(5) Ag(20)-Ag(21) 3.33(2) Ag(1)-Ag(12) 2.958(5) Ag(21)-Ag(37) 2.007(17) Ag(1)-Ag(37) 3.024(9) Ag(21)-S(16) 2.55(3) Ag(1)-Ag(8) 3.092(6) Ag(21)-Ag(28) 2.54(6) Ag(1)-Ag(34) 3.133(9) Ag(21)-S(4) 2.58(3) Ag(2)-Ag(50) 1.386(14) Ag(21)-S(8) 2.65(3) Ag(2)-Ag(37) 1.711(10) Ag(21)-Ag(33) 2.888(14) Ag(2)-Ag(38) 1.984(17) Ag(21)-Ag(50) 2.92(2) Ag(2)-S(8) 2.30(2) Ag(23)-Ag(47) 1.689(14) Ag(2)-Ag(45) 2.360(8) Ag(23)-Ag(19)#1 2.248(13) Ag(2)-Ag(30) 3.015(9) Ag(23)-Ag(28) 2.26(4) Ag(2)-Ag(32) 3.025(9) Ag(23)-S(16) 2.41(3) Ag(2)-Ag(10) 3.085(7) Ag(23)-Ag(7)#1 2.713(12) Ag(2)-Ag(3) 3.127(6) Ag(23)-Ag(52)#1 2.77(4) Ag(3)-Ag(32) 1.884(9) Ag(23)-Ag(39) 2.990(14) Ag(3)-Ag(25) 2.668(8) Ag(23)-Ag(48) 3.062(12) Ag(3)-Ag(45) 2.685(8) Ag(23)-Ag(24) 3.051(15) Ag(3)-Ag(6) 2.835(6) Ag(24)-Ag(39) 1.644(11) Ag(3)-Ag(6)#1 2.845(6) Ag(24)-Ag(12)#1 1.859(10) Ag(3)-Ag(12) 2.856(7) Ag(24)-Ag(29)#1 2.519(12) Ag(3)-Ag(12)#1 2.864(6) Ag(24)-Ag(19)#1 2.523(11) Ag(3)-Ag(5) 2.970(6) Ag(24)-Ag(25) 2.640(10) Ag(3)-Ag(13) 2.974(6) Ag(24)-Ag(11)#1 3.004(9) Ag(3)-Ag(14) 2.980(6) Ag(25)-Ag(39) 2.316(9) Ag(4)-Ag(32) 1.568(10) Ag(25)-Ag(50) 2.345(13) Ag(4)-Ag(42) 1.585(12) Ag(25)-Ag(32) 2.601(10) Ag(4)-Ag(46) 2.315(9) Ag(25)-Ag(43) 2.911(16) Ag(4)-S(1) 2.336(19) At(26)-At(53) 1.54(5) At(4)-At(44) 2.712(10) Ag(26)-S(9) 2.30(3) Ag(4)-S(7) 2.957(11) At(26)-At(52) 2.34(4) At(4)-At(18) 2.995(10) At(26)-S(17) 2.43(3) At(4)-At(13) 3.052(7) At(26)-At(44) 3.022(18) At(4)-At(5) 3.061(7) At(26)-At(31) 3.274(19) At(4)-At(30) 3.219(10) At(27)-At(34) 1.987(17) At(4)-At(16) 3.25(4) Ag(27)-S(6) 2.435(16) At(5)-At(24) 2.528(9) At(27)-S(14) 2.54(3) At(5)-At(29)#1 2.563(9) At(27)-At(45) 2.823(10) At(5)-At(46) 2.565(9) At(27)-S(9) 2.89(3) At(5)-At(25) 2.578(8) At(27)-At(53) 3.36(3) At(5)-At(32) 2.597(8) At(27)-At(30) 3.380(15) At(5)-At(12)#1 2.963(6) At(28)-At(47) 2.48(6) At(5)-At(6)#1 2.993(6) At(29)-At(35) 2.195(12) At(5)-At(39) 3.038(7) At(29)-At(24)#1 2.519(12) At(5)-At(35)#1 3.048(9) At(29)-At(5)#1 2.563(9) At(6)-At(48) 1.950(8) At(29)-At(36) 2.787(12) At(6)-At(33) 2.670(8) At(29)-At(40) 2.812(15) At(6)-At(46)#1 2.691(8) At(30)-At(38) 1.371(18) At(6)-At(12) 2.833(6) Ag(30)-S(1) 2.21(3) At(6)-At(3)#1 2.845(6) Ag(30)-S(6) 2.344(16) At(6)-At(12)#1 2.857(6) Age(30)-Age(45) 2.903(10) At(6)-At(14) 2.933(7) At(31)-At(53) 2.03(4) At(6)-At(13)#1 2.960(6) At(31)-S(17) 2.36(3) At(6)-At(49) 3.02(3) Ag(31)-S(12) 2.56(4) At(6)-At(5)#1 2.993(6) At(31)-S(14) 2.76(3) At(7)-At(48)#1 1.489(8) At(31)-At(47)#1 3.212(14) At(7)-At(49)#1 1.50(2) At(32)-At(46) 2.558(11) At(7)-At(52) 1.81(2) At(32)-At(45) 2.569(10) Ag(7)-S(5)#1 2.185(19) At(32)-At(44) 3.057(10) At(7)-At(19) 2.387(9) At(33)-At(37) 2.264(11) At(7)-At(23)#1 2.713(12) At(33)-At(48) 2.571(9) At(7)-At(47)#1 2.969(10) At(33)-At(49) 3.02(9) At(7)-At(13) 3.001(7) Ag(34)-S(14) 2.195(19) At(7)-At(14)#1 3.008(7) At(34)-At(45) 2.242(11) At(7)-At(44) 3.039(10) At(34)-At(53) 3.16(3) At(7)-At(26) 3.057(12) At(35)-At(51)#1 1.809(16) At(8)-At(51)#1 1.579(16) Ag(35)-S(13) 2.09(2) At(8)-At(35) 1.779(11) Ag(35)-Ag(36) 2.50(2) Ag(8)-S(13) 2.16(3) Ag(35)-Ag(5)#1 3.048(9) Ag(8)-Ag(33) 2.217(12) Ag(36)-S(11)#1 2.37(2) Ag(8)-Ag(49) 2.73(6) Ag(36)-O(1) 2.40(2) Ag(8)-Ag(15) 3.072(9) Ag(36)-Ag(40) 2.65(3) Ag(8)-Ag(48) 3.125(9) Ag(37)-Ag(50) 1.626(15) Ag(9)-S(3) 2.309(18) Ag(37)-S(8) 2.28(2) Ag(9)-O(1) 2.335(19) Ag(38)-S(6) 2.48(2) Ag(9)-Ag(29) 2.833(10) Ag(38)-S(1) 2.66(3) Ag(9)-Ag(35) 3.014(12) Ag(38)-Ag(45) 2.831(12) Ag(9)-Ag(11) 3.063(10) Ag(38)-Ag(50) 2.92(2) Ag(10)-S(3) 2.361(15) Ag(39)-Ag(43) 1.86(2) Ag(10)-S(6) 2.392(14) Ag(39)-S(12)#1 2.326(19) Ag(10)-Ag(45) 2.756(8) Ag(39)-Ag(40)#1 3.352(14) Ag(10)-Ag(34) 3.032(10) Ag(40)-S(12) 2.23(3) Ag(10)-Ag(38) 3.092(15) Ag(40)-O(1) 2.24(2) Ag(10)-Ag(27) 3.155(18) Ag(40)-Ag(39)#1 3.352(14) Ag(11)-Ag(34) 1.731(11) Ag(41)-Ag(49) 2.20(7) Ag(11)-Ag(29) 2.300(10) Ag(41)-S(7)#1 2.320(16) Ag(11)-S(14) 2.35(2) Ag(41)-S(10)#1 2.39(2) Ag(11)-Ag(40) 2.77(2) Ag(41)-S(5) 2.40(3) Ag(11)-Ag(24)#1 3.004(9) Ag(41)-Ag(46)#1 2.896(12) Ag(11)-Ag(12) 3.244(6) Ag(41)-Ag(51)#1 3.016(19) Ag(11)-Ag(31) 3.259(12) Ag(41)-Ag(44)#1 3.016(14) Ag(12)-Ag(24)#1 1.858(10) Ag(41)-Ag(7)#1 3.091(15) Ag(12)-Ag(19) 2.635(8) Ag(42)-S(7) 2.247(18) Ag(12)-Ag(29) 2.714(10) Ag(42)-S(10) 2.332(17) Ag(12)-Ag(6)#1 2.856(6) Ag(42)-S(1) 2.73(3) Ag(12)-Ag(3)#1 2.864(6) Ag(42)-Ag(46) 2.739(12) Ag(12)-Ag(5)#1 2.963(6) Ag(42)-Ag(44) 2.971(17) Ag(12)-Ag(13) 2.983(7) Ag(43)-S(2) 2.24(2) Ag(12)-Ag(14)#1 2.984(6) Ag(43)-S(12)#1 2.78(3) Ag(54)-Ag(13) 1.942(9) Ag(44)-S(7) 1.698(16) Ag(54)-Ag(45) 2.650(10) Ag(44)-S(9) 2.205(16) Ag(54)-Ag(19) 2.671(10) Ag(44)-Ag(46) 2.374(11) Ag(54)-Ag(24)#1 2.925(11) Ag(44)-Ag(41)#1 3.016(14) Ag(54)-Ag(48)#1 2.951(10) Ag(44)-Ag(48)#1 3.022(9) Ag(54)-Ag(32) 2.955(11) Ag(46)-Ag(51) 2.133(17) Ag(54)-Ag(34) 3.105(11) Ag(46)-Ag(49)#1 2.46(6) At(13)-At(44) 1.552(9) At(46)-At(48)#1 2.598(10) At(13)-At(48)#1 2.510(8) At(46)-At(6)#1 2.691(8) At(13)-At(32) 2.543(9) At(47)-At(52)#1 1.94(4) At(13)-At(45) 2.554(8) At(47)-S(17)#1 2.358(16) At(13)-At(46) 2.576(9) Ag(47)-S(16) 2.43(3) At(13)-At(19) 2.575(9) At(47)-At(19)#1 2.932(10) At(13)-At(6)#1 2.960(6) At(47)-At(7)#1 2.969(10) At(14)-At(23) 1.636(13) At(47)-At(31)#1 3.212(14) At(14)-At(48) 2.507(8) At(48)-At(49) 1.43(3) At(14)-At(33) 2.527(10) At(48)-At(7)#1 1.488(8) At(14)-At(25) 2.574(9) At(48)-At(13)#1 2.510(8) At(14)-At(19)#1 2.601(9) At(48)-At(19)#1 2.565(10) At(14)-At(24) 2.719(9) At(48)-At(46)#1 2.598(10) At(14)-At(12)#1 2.984(6) At(48)-At(54)#1 2.951(10) At(14)-At(7)#1 3.008(7) At(48)-At(51)#1 2.983(16) At(14)-At(37) 3.068(9) At(49)-At(7)#1 1.50(2) Ag(15)-S(4) 2.25(2) Ag(49)-S(5) 2.09(3) Ag(15)-S(3) 2.335(17) At(49)-At(51)#1 2.35(3) At(15)-At(33) 2.817(9) At(49)-At(46)#1 2.46(6) At(15)-At(37) 2.904(10) At(49)-At(44)#1 3.02(9) At(15)-At(21) 3.189(18) At(49)-At(52)#1 3.17(3) Ag(16)-S(1) 2.28(3) Ag(50)-S(8) 1.767(19) Ag(16)-S(2) 2.38(2) At(51)-At(8)#1 1.579(16) At(16)-At(17) 2.55(5) At(51)-At(35)#1 1.809(16) At(16)-At(25) 2.733(19) Ag(51)-S(13)#1 2.02(3) At(16)-At(50) 2.90(4) At(51)-At(49)#1 2.35(3) At(17)-At(43) 1.62(3) At(51)-At(48)#1 2.983(16) Ag(17)-S(2) 2.35(2) At(51)-At(41)#1 3.016(19) At(17)-S(11) 2.42(2) At(51)-At(6)#1 3.115(13) At(17)-At(25) 2.927(11) At(52)-At(47)#1 1.94(4) At(17)-At(39) 2.927(10) Ag(52)-S(17) 2.19(3) At(18)-At(42) 2.346(17) Ag(52)-S(5)#1 2.61(4) At(18)-S(11) 2.37(3) At(52)-At(23)#1 2.77(4) At(18)-S(10) 2.49(2) At(52)-At(53) 3.15(5) Age(18)-Age(46) 2.801(11) At(52)-At(49)#1 3.17(3) At(18)-At(51) 3.144(17) At(52)-At(48)#1 3.24(2) At(19)-At(23)#1 2.248(13) Ag(53)-S(14) 2.13(5) Ag(19)-Ag(24)#1 2.523(11) Ag(53)-S(17) 2.22(3) Ag(19)-Ag(48)#1 2.565(10) S(5)-Ag(7)#1 2.185(19) Ag(19)-Ag(14)#1 2.601(9) S(5)-Ag(52)#1 2.61(4) Ag(19)-Ag(52) 2.713(16) S(7)-Ag(41)#1 2.320(16) Ag(19)-Ag(53) 2.733(14) S(10)-Ag(41)#1 2.39(2) Ag(19)-Ag(31) 2.772(10) S(11)-Ag(36)#1 2.37(2) Ag(20)-Ag(28) 2.06(6) S(12)-Ag(39)#1 2.326(19) Ag(20)-S(2) 2.43(2) S(12)-Ag(43)#1 2.78(3) Ag(20)-S(16) 2.49(3) S(17)-Ag(47)#1 2.358(16) Ag(20)-Ag(25) 2.742(10) S(13)-Ag(51)#1 2.02(3)

[0047] Table 3: Important Bond Angles (°)

[0048] S(1)-Ag(4)-S(7) 111.4(6) Ag(42)-S(7)-S(9) 125.7(8) S(3)-Ag(9)-O(1) 160.4(6) Ag(41)#1-S(7)-S(9) 121.6(9) S(3)-Ag(10)-S(6) 156.8(5) S(10)-S(7)-S(9) 162.2(8) S(1)-Ag(16)-S(2) 168.1(9) Ag(44)-S(7)-Ag(46) 56.3(4) S(2)-Ag(17)-S(11) 167.3(8) Ag(42)-S(7)-Ag(46) 63.7(4) S(11)-Ag(18)-S(10) 164.7(7) Ag(41)#1-S(7)-Ag(46) 67.3(4) S(2)-Ag(20)-S(16) 159.4(8) S(10)-S(7)-Ag(46) 80.5(5) S(16)-Ag(21)-S(4) 111.6(10) S(9)-S(7)-Ag(46) 117.3(6) S(16)-Ag(21)-S(8) 112.6(11) Ag(44)-S(7)-Ag(4) 64.8(4) S(6)-Ag(27)-S(14) 139.9(12) Ag(42)-S(7)-Ag(4) 31.9(3) S(6)-Ag(27)-S(9) 117.0(10) Ag(41)#1-S(7)-Ag(4) 111.6(5) S(14)-Ag(27)-S(9) 101.8(9) S(10)-S(7)-Ag(4) 88.0(5) S(1)-Ag(30)-S(6) 168.0(8) S(9)-S(7)-Ag(4) 104.9(6) S(17)-Ag(31)-S(12) 139.8(10) Ag(46)-S(7)-Ag(4) 47.0(2) S(17)-Ag(31)-S(14) 107.5(10) Ag(50)-S(8)-Ag(37) 45.1(6) S(12)-Ag(31)-S(14) 112.2(8) Ag(50)-S(8)-Ag(2) 37.1(6) S(11)#1-Ag(36)-O(1) 149.2(13) Ag(37)-S(8)-Ag(2) 43.9(4) S(6)-Ag(38)-S(1) 123.6(10) Ag(50)-S(8)-Ag(21) 80.0(10) S(6)-Ag(38)-Ag(45) 77.5(4) Ag(37)-S(8)-Ag(21) 47.2(6) S(1)-Ag(38)-Ag(45) 98.5(6) Ag(2)-S(8)-Ag(21) 91.1(7) S(12)-Ag(40)-O(1) 164.1(9) Ag(44)-S(9)-Ag(26) 84.2(8) S(7)#1-Ag(41)-S(10)#1 58.8(6) Ag(44)-S(9)-S(7) 42.3(5) S(7)#1-Ag(41)-S(5) 128.2(12) Ag(26)-S(9)-S(7) 108.4(10) S(10)#1-Ag(41)-S(5) 170.8(8) Ag(44)-S(9)-Ag(27) 95.2(7) S(7)-Ag(42)-S(10) 60.6(6) Ag(26)-S(9)-Ag(27) 88.9(9) S(7)-Ag(42)-S(1) 123.4(8) S(7)-S(9)-Ag(27) 128.5(8) S(10)-Ag(42)-S(1) 161.2(7) S(7)-S(10)-Ag(42) 57.9(6) S(7)-Ag(44)-S(9) 76.8(8) S(7)-S(10)-Ag(41)#1 59.1(6) S(17)#1-Ag(47)-S(16) 164.2(7) Ag(42)-S(10)-Ag(41)#1 103.6(7) S(17)-Ag(52)-S(5)#1 158.0(12) S(7)-S(10)-Ag(18) 104.3(6) S(14)-Ag(53)-S(17) 144(3) Ag(42)-S(10)-Ag(18) 58.1(6) Ag(30)-S(1)-Ag(16) 128.3(16) Ag(41)#1-S(10)-Ag(18) 103.9(6) Ag(30)-S(1)-Ag(4) 90.1(7) Ag(18)-S(11)-Ag(36)#1 103.0(10) Ag(16)-S(1)-Ag(4) 89.6(13) Ag(18)-S(11)-Ag(17) 105.8(8) Ag(30)-S(1)-Ag(38) 31.0(5) Ag(36)#1-S(11)-Ag(17) 121.0(10) Ag(16)-S(1)-Ag(38) 98.6(16) Ag(40)-S(12)-Ag(39)#1 94.7(8) Ag(4)-S(1)-Ag(38) 99.7(7) Ag(40)-S(12)-Ag(31) 104.0(13) Ag(30)-S(1)-Ag(42) 102.3(8) Ag(39)#1-S(12)-Ag(31) 91.6(9) Ag(16)-S(1)-Ag(42) 106.7(18) Ag(40)-S(12)-Ag(43)#1 101.6(14) Ag(4)-S(1)-Ag(42) 35.4(4) Ag(39)#1-S(12)-Ag(43)#1 41.7(6) Ag(38)-S(1)-Ag(42) 125.5(8) Ag(31)-S(12)-Ag(43)#1 128.1(11) Ag(43)-S(2)-Ag(17) 41.1(9) Ag(51)#1-S(13)-C(44) 155(3) Ag(43)-S(2)-Ag(16) 97.5(15) Ag(51)#1-S(13)-Ag(35) 52.2(6) Ag(17)-S(2)-Ag(16) 65.3(16) Ag(51)#1-S(13)-Ag(8) 44.2(6) Ag(43)-S(2)-Ag(20) 80.2(10) Ag(35)-S(13)-Ag(8) 49.5(5) Ag(17)-S(2)-Ag(20) 106.8(6) Ag(53)-S(14)-Ag(34) 93.8(9) Ag(16)-S(2)-Ag(20) 93.9(10) Ag(53)-S(14)-Ag(11) 105.1(9) Ag(9)-S(3)-Ag(15) 113.2(7) Ag(34)-S(14)-Ag(11) 44.6(4) Ag(9)-S(3)-Ag(10) 104.4(6) Ag(53)-S(14)-Ag(27) 91.8(15) Ag(15)-S(3)-Ag(10) 106.5(6) Ag(34)-S(14)-Ag(27) 49.0(6) Ag(15)-S(4)-Ag(21) 82.4(7) Ag(11)-S(14)-Ag(27) 92.3(7) Ag(40)-O(1)-Ag(9) 99.8(8) Ag(53)-S(14)-Ag(31) 46.9(11) Ag(40)-O(1)-Ag(36) 69.5(9) Ag(34)-S(14)-Ag(31) 101.1(7) Ag(9)-O(1)-Ag(36) 93.3(8) Ag(11)-S(14)-Ag(31) 78.7(7) Ag(49)-S(5)-Ag(7)#1 41.1(7) Ag(27)-S(14)-Ag(31) 131.1(9) Ag(49)-S(5)-Ag(41) 58(2) Ag(52)-S(17)-Ag(53) 91.0(15) Ag(7)#1-S(5)-Ag(41) 84.7(7) Ag(52)-S(17)-Ag(47)#1 50.4(12) Ag(49)-S(5)-Ag(52)#1 84.0(11) Ag(53)-S(17)-Ag(47)#1 112.7(6) Ag(7)#1-S(5)-Ag(52)#1 43.3(7) Ag(52)-S(17)-Ag(31) 107.8(7) Ag(41)-S(5)-Ag(52)#1 108.5(14) Ag(53)-S(17)-Ag(31) 52.5(14) Ag(30)-S(6)-Ag(10) 103.4(5) Ag(47)#1-S(17)-Ag(31) 85.7(7) Ag(30)-S(6)-Ag(27) 90.0(7) Ag(44)-S(7)-S(9) 60.9(6) Ag(10)-S(6)-Ag(27) 81.6(6) Ag(52)-S(17)-Ag(26) 60.5(13) Ag(30)-S(6)-Ag(38) 32.9(5) Ag(53)-S(17)-Ag(26) 38.2(14) Ag(10)-S(6)-Ag(38) 78.8(6) Ag(47)#1-S(17)-Ag(26) 102.8(7) Ag(27)-S(6)-Ag(38) 107.7(6) Ag(31)-S(17)-Ag(26) 86.1(7) Ag(44)-S(7)-Ag(42) 96.7(6) Ag(23)-S(16)-Ag(47) 40.8(6) Ag(44)-S(7)-Ag(41)#1 96.1(7) Ag(23)-S(16)-Ag(20) 72.3(9) Ag(42)-S(7)-Ag(41)#1 108.6(6) Ag(47)-S(16)-Ag(20) 98.6(11) Ag(44)-S(7)-S(10) 136.8(7) Ag(23)-S(16)-Ag(21) 99.1(8) Ag(42)-S(7)-S(10) 61.5(6) Ag(47)-S(16)-Ag(21) 134.1(12) Ag(41)#1-S(7)-S(10) 62.0(6) Ag(20)-S(16)-Ag(21) 82.7(9)

[0049] Note: Symmetrical code: #1 -x+1, y, -z+3 / 2.

[0050] Other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention that follow the general principles of the invention and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of the invention are indicated by the following claims.

[0051] It should be understood that the present invention is not limited to the precise structure described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of the invention is limited only by the appended claims.

Claims

1. A method for preparing a super-large silver thiol cluster material constructed with a silver triangle as its core, characterized in that, The silver cluster material is made of and Synthesized, its chemical formula is: ; The silver cluster material belongs to the triclinic crystal system, with space group P-1 and cell parameters [missing information]. , ; The specific method for preparing the silver cluster material is as follows: Step 1: and Dissolved in a solvent, a solvothermal reaction is performed to obtain a dark red suspension; Step 2: After filtering the dark red suspension, a dark red transparent solution is obtained. The dark red transparent solution is then evaporated until dark red blocky crystals are obtained. The solvent is a mixed solution of isopropanol, dichloromethane, and N,N-dimethylformamide in a volume ratio of 1:1:1; The and The molar ratio is 2.5:1.0; The solvothermal reaction temperature is 65 °C, and the reaction time is 2880 minutes.

2. The method for preparing a super-large silver thiol cluster material with a silver triangle as its core according to claim 1, characterized in that, The pH value of the dark red suspension is 6.

0.

3. The method for preparing a super-large silver thiol cluster material with a silver triangle as its core according to claim 1, characterized in that, The volatilization temperature of the deep red transparent solution is room temperature.

4. The method for preparing a super-large silver thiol cluster material with a silver triangle as its core according to claim 1, characterized in that, The silver cluster material has luminescent properties.

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