阅读说明：本技术 基于十四核银纳米团簇的二维晶态超电电极材料及其制备方法和应用 (Two-dimensional crystalline state super-electrode material based on fourteen-core silver nanoclusters and preparation method and application thereof ) 是由 诸葛婧 吴登泽 奚云红 闫鑫 胡茂林 于 2020-11-10 设计创作，主要内容包括：本发明提供一种基于十四核银纳米团簇的二维晶态超电电极材料及其制备方法和应用,属于银簇合物制备技术领域。在常温下,依次向DMF中,加入AgSPr~i、AgTFA、AgOTF、全氟壬二酸及Me_4NOH的甲醇溶液,充分混合均匀后,于密闭容器中,加热反应,过滤挥发得到浅黄色的菱形晶体,即为所述基于十四核银纳米团簇的二维晶态超电电极材料。电化学研究表明,该电级材料具有优良的电容特性和良好的电化学可逆性,在4.5 A·g~(-1)的电流密度下的最高比电容为372 F·g~(-1),经过6000次循环充放电后,电容仅衰减为原来的95%,证实该材料是一种具有高比电容和长循环稳定性的超电电极材料。(The invention provides a fourteen-core silver nanocluster-based two-dimensional crystalline state super-electrode material and a preparation method and application thereof, and belongs to the technical field of silver cluster compound preparation. Sequentially adding AgSPr to DMF at normal temperature i AgTFA, AgOTF, perfluoroazelaic acid and Me 4 And (3) fully and uniformly mixing NOH methanol solution, heating and reacting in a closed container, filtering and volatilizing to obtain light yellow rhombic crystals, namely the fourteen-core silver nanocluster-based two-dimensional crystalline state super electrode material. Electrochemical research shows that the electrode material has excellent capacitance characteristic and good electrochemical reversibility at 4.5 A.g ‑1 Has a maximum specific capacitance of 372F g at a current density of ‑1 After 6000 times of cyclic charge and discharge, the capacitance is only attenuated to 95 times of the original capacitance% proves that the material is a super-electric electrode material with high specific capacitance and long cycle stability.)

1. The two-dimensional crystalline state super-electrode material based on the fourteen-core silver nanoclusters is characterized by having a chemical formula as follows: [ Ag ]₁₄(Sprⁱ)₆(C₉F₁₄O₄)₄(DMF)₈]_∞Belonging to the triclinic system, the space group is P ī, and the cell parameters are:

α＝95.979(2)°，β＝114.333(2)°，γ＝91.691(3)°。

2. a method for preparing the fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material of claim 1, wherein the method comprises the following steps: the method comprises the following steps:

a. in DMF, AgSPr is addedⁱAgTFA and AgOTF, fully dissolving to obtain a solution a;

b. adding perfluoroazelaic acid into the solution A to obtain a colorless solution B;

c. addition of Me to the colorless solution B₄Methanol solution of NOH to obtain solution C;

d. sealing the solution C, heating to 65-80 ℃, and continuously reacting for 18-25 h to obtain a light yellow solution D;

e. and filtering the solution D, naturally volatilizing the filtrate at the temperature of 2-10 ℃, and obtaining a large amount of light yellow rhombic crystals which are the two-dimensional crystalline state super-electrode material based on the fourteen-core silver nanoclusters.

3. The method for preparing the fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material of claim 2, wherein in the step d, the solution C is sealed and heated to 70 ℃ for 20 hours of reaction, and the fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material is prepared.

4. The method for preparing the fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material of claim 2 or 3, wherein in step a, AgTFA, AgOTF and AgSPrⁱThe amount ratio of the substances of (a) is 1:1: 1.

5. The method for preparing a fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material of claim 4, wherein in step b, perfluoroazelaic acid and AgSPrⁱThe amount ratio of the substances of (a) is 1: 1.

6. The method for preparing a fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material of claim 2, wherein in step c, Me is added to the colorless solution B at a concentration of 0.1mol/L₄Methanol solution of NOH to obtain solution C.

7. The method for preparing a fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material of claim 2, wherein in steps a, b and c, the substances are mixed at ambient temperature and with the aid of ultrasonic waves.

8. The method for preparing the fourteen-core silver nanocluster-based two-dimensional crystalline state microelectrode material of claim 2, wherein in the step e, after the solution D is filtered, the filtrate is placed at a temperature of 5 ℃ for natural volatilization for 1 week, and a large number of light yellow rhombohedral crystals appear, namely the fourteen-core silver nanocluster-based two-dimensional crystalline state microelectrode material.

9. Use of the fourteen-core silver nanocluster-based two-dimensional crystalline supercapacitor electrode material of claim 1 as an electrode material for a supercapacitor.

Technical Field

The invention belongs to the technical field of preparation of silver cluster compounds, and particularly relates to a fourteen-core silver nanocluster-based two-dimensional crystalline state super-electrode material and a preparation method and application thereof.

Background

Designing and constructing compounds from the molecular level is a key way for developing novel functional materials. Metal cluster compounds, especially poly-cluster compounds (or MOCs, cluster-based metal organic framework compounds), have received much attention from researchers due to their excellent photoelectric and porous properties, which are distinguished from isolated cluster compounds, and the design and development of poly-cluster compounds with potential application prospects is an important direction in the current research of photoelectric functional materials. The individual cluster building blocks of a multiple cluster can be viewed as a special molecule formed by coordination interactions between organic ligands and metal atoms and metal-metal interactions. These single cluster building blocks can be connected by organic bridging ligands to form metal-organic framework structures with different dimensions (2D/3D). Therefore, the poly-cluster compound not only keeps the characteristics of the cluster compound in the aspects of structure, light absorption, electric conduction and the like, but also has the characteristics of the metal organic framework material in the aspects of pore structure, adsorption and the like. The multi-cluster compound has the characteristics of designable structure and adjustable performance, and has wide research and application prospects in the field of photoelectric materials as a special crystalline molecular material with accurate atomic structure.

The formation process of the coin metal poly-cluster compound, particularly the high-nuclear silver poly-cluster compound, is very complex, and relates to complex self-assembly processes of coordination polymerization of silver ions and bridging ligands, silver-silver interaction, coordination reaction of silver ions and protecting ligands and the like. Obtaining high nuclear silver polymeric clusters is difficult due to lack of adequate understanding of the mechanism of formation of the high nuclear silver polymeric clusters. Therefore, on the basis of the previous research on the construction, structure and performance of the one-dimensional high-nuclear silver multi-cluster compound, the high-nuclear silver multi-cluster compound with the multi-dimensional structure is further constructed by introducing a polyfluoric diacid flexible bridging ligand into a system, and the high-nuclear silver multi-cluster compound is used as a super-capacitor electrode material to research the super-electric performance of the high-nuclear silver multi-cluster compound. Related research can further enrich the variety of the high-nuclear silver poly-cluster compound and lay a research foundation for the application of the high-nuclear silver poly-cluster compound in photoelectric materials, particularly super-capacitor electrode materials.

Disclosure of Invention

In view of this, the invention provides a two-dimensional crystalline state super-electrode material based on fourteen-core silver nanoclusters, so as to expand the types of high-core silver multi-cluster compounds and provide a reference for research on the high-core silver multi-cluster compounds.

The invention also provides a preparation method of the two-dimensional crystalline state super-electrode material based on the fourteen-core silver nanoclusters, which is simple in process and provides guidance for controlling and synthesizing the high-core silver nanocluster compound.

The invention also provides application of the fourteen-core silver nanocluster-based two-dimensional crystalline state super electrode material as an electrode material of a super capacitor.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a two-dimensional crystalline state super-electrode material based on fourteen-core silver nanoclusters has a chemical formula as follows:

[Ag₁₄(SPrⁱ)₆(C₉F₁₄O₄)₄(DMF)₈]_∞belonging to the triclinic system, the space group is P ī, and the cell parameters are:

α＝95.979(2)°，β＝114.333(2)°，γ＝91.691(3)°。

a method for preparing the fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material comprises the following steps:

a. in DMF, AgSPr is addedⁱAgTFA and AgOTF, fully dissolving to obtain a solution a;

b. adding perfluoroazelaic acid into the solution A to obtain a colorless solution B;

c. addition of Me to the colorless solution B₄Methanol solution of NOH to obtain solution C;

d. sealing the solution C, heating to 65-80 ℃, and continuously reacting for 18-25 h to obtain a light yellow solution D;

e. and filtering the solution D, naturally volatilizing the filtrate at the temperature of 2-10 ℃, and obtaining a large amount of light yellow rhombic crystals which are the two-dimensional crystalline state super-electrode material based on the fourteen-core silver nanoclusters.

Preferably, in the step d, the solution C is sealed and heated to 70 ℃ for 20 hours of reaction, and the fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material is prepared.

Preferably, in step a, AgTFA, AgOTF and AgSPrⁱThe amount ratio of the substances of (a) is 1:1: 1.

Preferably, in step b, perfluoroazelaic acid and AgSPrⁱThe amount ratio of the substances of (a) is 1: 1.

Preferably, in step c, Me is added to the colorless solution B in a concentration of 0.1mol/L₄Methanol solution of NOH to obtain solution C.

Preferably, in step a, step b and step c, the substances are mixed at ambient temperature with the aid of ultrasound.

Preferably, in the step e, after the solution D is filtered, the filtrate is placed at a temperature of 5 ℃ for natural volatilization for 1 week, and a large number of light yellow rhombohedral crystals appear, that is, the fourteen-core silver nanocluster-based two-dimensional crystalline state microelectrode material

The application of the fourteen-core silver nanocluster-based two-dimensional crystalline super electrode material as an electrode material of a super capacitor.

According to the technical scheme, the invention provides a fourteen-core silver nanocluster-based two-dimensional crystalline state super-electrode material, and a preparation method and application thereof, and the two-dimensional crystalline state super-electrode material has the following beneficial effects: sequentially adding AgSPr to DMF at normal temperatureⁱAgTFA, AgOTF, perfluoroazelaic acid and Me₄And (2) sufficiently and uniformly mixing NOH methanol solution, heating and reacting in a closed container for a period of time, filtering, and naturally volatilizing the filtrate to obtain light yellow rhombic crystals, namely the fourteen-nucleus silver nanocluster-based two-dimensional crystalline state super-electrode material (SSc-3 for short). The results of X-ray single crystal diffraction analysis showed that SSc-3 crystallized in the triclinic system with the space group P ī. The high nuclear silver polymer clusterThe central skeleton of the structural unit consists of 14 silver ions and 6 SPrsⁱThe protective ligand consists of two perfluoroazelaic acid bridging anions and four DMF molecules coordinated with a single silver atom at the periphery. Electrochemical experiments show that SSc-3 has good capacitance characteristic and good electrochemical reversibility and the current density is 4.5 A.g^-1When the maximum specific capacitance is 372F g^-1. After 6000 charge-discharge cycles, the capacitance of the electrode material can still keep 95% of the initial value, which shows that SSc-3 has good cycle stability as a super-capacitor electrode material.

Drawings

FIG. 1 is a schematic representation of the molecular structure of SSc-3 (hydrogen omitted for clarity).

FIG. 2 is a schematic diagram of a two-dimensional network structure of SSc-3.

FIG. 3 is a schematic diagram of a 2D structure with SSc-3 extended in the a x c direction.

FIG. 4 is an XRD pattern of SSc-3.

FIG. 5 is a solid state infrared spectrum of SSc-3.

FIG. 6 is a TGA spectrum of SSc-3.

FIG. 7 is an SEM image of SSc-3.

FIG. 8 is a CV curve for SSc-3 at low scan rates.

FIG. 9 is a CV curve for SSc-3 at high scan rates.

FIG. 10 is a cyclic voltammetry curve for SSc-3.

FIG. 11 is a constant current charge/discharge curve for SSc-3.

FIG. 12 is the cycle stability of SSc-3 over the first 30 cycles.

FIG. 13 is the cycling stability of SSc-3 over 6000 cycles.

FIG. 14 is an SSc-3 Nyquist diagram and corresponding equivalent circuit.

FIG. 15 is a Bode phase diagram of SSc-3.

FIG. 16 is an XRD pattern of SSc-3 after 5000 charge/discharge cycles.

FIG. 17 is an SEM image of SSc-3 after 5000 charge/discharge cycles.

Detailed Description

The technical scheme and the technical effect of the invention are further elaborated in the following by combining the drawings of the invention.

Referring to fig. 1 to 3, in one embodiment, a fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material has a chemical formula: [ Ag ]₁₄(Sprⁱ)₆(C₉F₁₄O₄)₄(DMF)₈]_∞Belonging to the triclinic system, the space group is P ī, and the cell parameters are:α＝95.979(2)°，β＝114.333(2)°，γ＝91.691(3)°。

the fourteen-core silver nanocluster-based two-dimensional crystalline state super-electrode material is prepared from perfluoroazelaic acid and AgSPrⁱ(silver isopropyl sulfide), AgTFA (silver trifluoroacetate) and AgOTF (silver trifluoromethanesulfonate) in DMF (N, N-dimethylformamide) and Me₄And (3) reacting in methanol solution of NOH (tetramethylammonium hydroxide) with the help of ultrasonic waves to form the two-dimensional polymer cluster compound based on the 14-core silver nanocluster.

According to the results of single crystal X-ray diffraction analysis, the cluster compound had a triclinic system of space group P ī. The central skeleton of the single structural unit of the high-nuclear silver multi-cluster compound consists of 14 silver ions and 6 SPrsⁱThe protective ligand consists of two tetradecafluorononanedioic acid bridging anions and four DMF molecules coordinated with a single silver atom at the periphery. In its core skeleton, the distance range of interaction of Ag … Ag is The distance range of interaction of Ag … S is Bridged perfluoroazelaic acid anion through (. mu.m)₅-η¹,η²,η¹,η¹) And (mu)₄-η¹,η¹,η¹,η¹) The two modes coordinate with silver ions on the cluster skeleton; tert-butyl sulfide SPrⁱThe coordination modes of the protecting ligands are respectively (mu)₅-η¹,η¹,η¹,η¹,η¹)，(μ₄-η¹,η¹,η¹,η¹) And (mu)₃-η¹,η¹,η¹). Each building block of the polymeric cluster is surrounded by eight DMF molecules and eight carboxylates. These ligands serve as shells to protect the formation of multiple clusters. SSc-3 is a two-dimensional layered structure (viewed from the b-axis), with the layers being placed side-by-side without intervening layers.

The crystal data and structure refinement data for SSc-3 are shown in Table 1.

TABLE 1 Crystal data and Structure refinement parameters for SSc-3

^aR₁＝[Σabs(abs(Fo)-abs(Fc))]/[Σabs(Fo)].^bwR2＝[Σ(w(Fo²-Fc²)²)/Σ[w(Fo²)²]^0.5.

As shown in fig. 4, the simulated XRD pattern obtained from SSc-3 crystallographic data was substantially identical to the XRD pattern experimentally measured from the powder sample, indicating that the prepared sample was of higher purity.

FIG. 5 is an infrared spectrum of SSc-3. In the infrared spectrum, 2950cm^-1The absorption band is (C-H) telescopic vibration of 1675cm^-1The absorption band at position (D) is related to (C ═ O) stretching vibration at 1393cm^-1And 1204cm^-1Coupled vibration with absorption bands of (COH) and (CO), and vibration absorption bands of (C-F) and (C-C) appear at 1160cm^-1And 814cm^-1To (3). 664cm^-1Absorption band ofBending modes ascribed to δ (C-O) and δ (C ═ O), and 540cm^-1The absorption bands of (C-O) are related to (COO) and (C-O) vibrations.

Referring to fig. 6, the thermal stability of the cluster SSc-3 was studied by thermogravimetry, and the decomposition process of the cluster is divided into two steps: a first step of losing DMF molecules and a fraction of organic ligands at about 100 ℃; in the second step, the organic fraction is completely decomposed at 227 ℃. The final residue is about Ag₂39.7% of O is close to the theoretical calculation of 37.8%.

In FIG. 6, the crystal of SSc-3 is inserted and the crystal is a rhombohedral pale yellow. Referring also to FIG. 7, the SEM image of SSc-3 shows that SSc-3 has a wide band-like structure, and is randomly stacked together with many thin sheets having a thickness of several nanometers, which indicates that SSc-3 has a large specific surface area. The special morphology is beneficial to improving the specific capacitance of the material and is beneficial to the occurrence of an oxidation-reduction process. Meanwhile, the high-nuclear silver cluster, the two-dimensional layer shape, the special appearance, the obvious conductivity and the very strong interaction between Ag/Ag and Ag/S promote the structural stability of SSc-3.

To further study the stability of the samples, SSc-3 was soaked in electrolyte (KOH,4M) for 4h, separated by centrifugation, and dried at room temperature. The obtained treated sample and the simulated XRD pattern of the sample are in good agreement. And, the electrolyte after soaking is analyzed by inductively coupled plasma spectroscopy, which shows that the silver ions released by the sample are few (less than 3%), and the SSc-3 is proved to have better stability in the selected electrolyte.

Referring collectively to fig. 8-9, the electrochemical performance of SSc-3 as a supercapacitor electrode material was characterized in a three-electrode system. The potential range of CV (cyclic voltammetry) test is between 0 and +1V, and the sweep rate range is 50mV s^-1To 1000 mV. s^-1. The charge build-up under the CV curve is caused by the double layer capacitance at the electrode surface and the redox process. The redox peak in the potential range of 0.25 to 0.6V is mainly related to the oxidation of silver in the alkaline electrolyte. Referring to FIGS. 10 and 11, at higher scan rates (from 50 mV. s)^-1～1000mV·s^-1) The induced potential peak is buried under the very large double layer current of the electrode. In addition to this, the present invention is,due to the internal resistance of the electrodes, the oxidation potential and the reduction potential are dislocated in the positive and negative directions. The CV curve of FIG. 10 is 600mV · s^-1Is obtained at different operating voltages. The semi-rectangular shape of all CV curves shows the electric double layer capacitance portion of SSc-3 at different operating voltages. The high symmetry of the potential window further confirms that SSc-3 has good capacitive properties and good electrochemical reversibility.

It is worth mentioning that the working electrode is prepared in the following way: the paint is prepared by mixing SSc-3, acetylene black and a binder (polytetrafluoroethylene) in a mass ratio of 80:15: 5. Depositing the obtained viscous slurry at 1 × 1cm²And performing electrochemical test on the foam nickel with the size under the pressure of 10MPa and the vacuum drying at 80 ℃ for 10 h. It is noted that the weight of the active electrode material is in the range of 1 to 1.2 mg.

The specific Capacitance (CSP) of the SSc-3 electrode was calculated from a constant current charge/discharge curve (FIG. 11) according to equation (1), where the discharge current, discharge time, voltage difference over the application time, and the indicated electrode mass are denoted by "I" (A), "Δ t"(s), "Δ V" (V), and "m" (g), respectively.

CSP ═ I × Δ t/Δ V × m (formula 1)

SSc-3 at 4.5Ag^-1The maximum specific capacitance provided is 372Fg^-1Calculated CSP at 6, 8, 11 and 13A is 365F g^-1、360F·g^-1、340F·g^-1And 325F g^-1. SSc-3 electrode at 11Ag^-1The first 30 charge/discharge curves of (a) are shown in fig. 12. In addition, 6000 cycles (0-1V, 11A. g) were investigated^-1) The high nuclear silver polymer cluster compound has the cycling stability. As shown in fig. 13, the initial CSP remained 95% after 6000 charge-discharge cycles, which confirms the long cycle life stability of the SSc-3 supercapacitor.

The conductivity of SSc-3 in the solid state was measured using a four-probe method. Before the measurement, the pressed tray (diameter 1cm, thickness 0.2mm) was kept at 100 ℃ for 4 hours, and the electrical conductivity of SSc-3 was measured to be 2.3 S.cm^-1. As shown in FIG. 14, on the other hand, the EIS technique was used to study the transport of SSc-3 electrochemical behaviorKinetics. Nyquist plots (fitting range 50kHz to 50mHz) of the prepared samples show two semicircular trends corresponding to the two interfacial charge transport processes. The first half circle of the high frequency region is attributable to the total charge transport resistance (R) of the electrode/electrolyte interface_ct1) While the second half of the middle frequency region is the total charge transport resistance (R) of the SSc-3 platelet internal interface_ct2). In addition, the minute semi-circle also confirms that the ion diffusion speed between the electrode and the electrolyte is fast. Similarly, the Warburg impedance (W) in the Nyquist plot of SSc-3 is related to OH^-The diffusion of ions is relevant. Likewise, the bode phase diagram shows the variation of the phase angle versus the applied frequency. As shown in fig. 15, the ideal capacitive behavior at a phase angle close to 80 ° indicates that SSc-3 electrodes can be considered as supercapacitor electrode materials with potential application value. The excellent supercapacitor performance of SSc-3 is associated with its suitable surface area and low resistance (good conductivity), which facilitates electron transport.

Further, the energy density E (Wh/kg) and the power density P (W/kg) of SSc-3 are respectively calculated by the following formulas:

E＝(C×V²)/(2×3.6)；

P＝(3600×E)/Δt；

wherein V (V) and Δ t(s) represent the operating voltage window (V) and the discharge time, respectively. The energy density of the SSc-3 electrode material measured in a KOH (4M) electrolyte solution was 51.6Wh kg^-1The power density is 2.32 kW.kg^-1. In order to evaluate the use performance of the electrode material, XRD and SEM analyses were further performed on the electrode material after use. As shown in fig. 16, 17, the XRD patterns remained substantially consistent, indicating that the electrode material was stable under the above conditions. This stability may result from the presence of CF on the outer surface of SSc-3₂The reason for the group. The excellent super-electric performance of the SSc-3 super-capacitor electrode material mainly comes from high electric conductivity and special appearance, and the high-nuclear silver poly-cluster compound has the common accumulation of unique electric double layer capacitance and pseudo-capacitance characteristics different from those of a common non-hybrid electrode material.

In conclusion, the invention firstly prepares the two-dimensional crystalline state super-electric electrode material [ Ag ] based on the fourteen-core silver nanoclusters₁₄(SPrⁱ)₆(C₉F₁₄O₄)₄(DMF)₈]_∞. Perfluoroazelaic acid as a bridging ligand connects the homonuclear silver cluster units to each other. The function of such ligands is important both structurally and in the potential applications of supercapacitors and the like. The conductive high-nuclear silver poly cluster compound has high specific capacitance (372F g)^-1) And long cycle life (retention over 6000 cycles maintained 95%). The excellent super-electric performance of the SSc-3 super-capacitor electrode material can be attributed to the high electric conductivity and special morphology of the electrode material. These results open up a new field of high performance supercapacitor electrode materials based on high nuclear silver polycluster compounds.

In another embodiment, the method for preparing the fourteen-core silver nanocluster-based two-dimensional crystalline microelectrode material comprises the following steps:

a. in DMF, AgSPr is addedⁱAgTFA and AgOTF, fully dissolving to obtain a solution a;

b. adding perfluoroazelaic acid into the solution A to obtain a colorless solution B;

c. addition of Me to the colorless solution B₄Methanol solution of NOH to obtain solution C;

d. sealing the solution C, heating to 65-80 ℃, and continuously reacting for 18-25 h to obtain a light yellow solution D;

e. and filtering the solution D, and naturally volatilizing at the temperature of 2-10 ℃ to obtain a large amount of light yellow rhombic crystals, namely the fourteen-core silver nanocluster-based two-dimensional crystalline state super-electrode material.

Specifically, AgSPr is added into DMF according to the mass ratio of 1:1:1ⁱThe AgTFA and the AgOTF are fully dissolved by ultrasonic to obtain a solution A; adding perfluoroazelaic acid into the solution A to obtain a colorless solution B, wherein AgSPrⁱAgTFA, AgOTF and perfluoroazelaic acid in a mass ratio of 1:1:1: 1; to the resulting colorless solution was added 0.1mol/L Me₄CH of NOH₃Sealing the solution with OH solution, heating to 65-80 deg.C, reacting for 18-25 hr, filtering the solution D, and standing at 2-10 deg.CAnd volatilizing to obtain a large number of light yellow rhombic crystals, namely the fourteen-core silver nanocluster-based two-dimensional crystalline state super-electrode material.

In one example, 0.264g (0.6mmol) of perfluoroazelaic acid and 0.110g (0.6mmol) of AgSPr were added to 10mL of DMFⁱAfter sufficiently dissolving with ultrasound, 0.132g (0.6mmol) of AgTFA and 0.154g (0.6mmol) of AgOTF were added, and 5 mM ME was added to the resulting colorless solution₄NOH(0.1mol/L，CH₃OH), sealing the solution, heating to 65 deg.C for 25 hr, filtering, and naturally volatilizing the filtrate at 2 deg.C for 5 days to obtain 28.7mg yellow rhombohedral crystal [ Ag ]₁₄(Sprⁱ)₆(C₉F₁₄O₄)₄(DMF)₈]_∞. Yield 6.7% (based on AgSPr)ⁱ)。

In one example, 0.132g (0.3mmol) of perfluoroazelaic acid and 0.055g (0.3mmol) of AgSPr were added to 3mL of DMFⁱAfter the mixture was sufficiently dissolved by sonication, 0.066g (0.3mmol) of AgTFA and 0.077g (0.3mmol) of AgOTF were added, and 1 mM ME was added to the resulting colorless solution₄NOH(0.1mol/L，CH₃OH), sealing the solution, heating to 70 deg.C for 20 hr, filtering, and naturally volatilizing the filtrate at 5 deg.C for 1 week to obtain 15.3mg yellow rhombohedral crystal [ Ag ]₁₄(Sprⁱ)₆(C₉F₁₄O₄)₄(DMF)₈]_∞. Yield 7.1% (based on AgSPr)ⁱ)。

In one example, 1.32g (3mmol) of perfluoroazelaic acid and 0.55g (3mmol) of AgSPr were added to 50mL of DMFⁱAfter the mixture was sufficiently dissolved by sonication, 0.66g (3mmol) of AgTFA and 0.77g (3mmol) of AgOTF were added, and 20 mM ME was added to the resulting colorless solution₄NOH(0.1mol/L，CH₃OH), sealing the solution, heating to 80 deg.C for 18 hr, filtering, and naturally volatilizing the filtrate at 10 deg.C for 15 days to obtain 162.3mg yellow rhombohedral crystal [ Ag ]₁₄(Sprⁱ)₆(C₉F₁₄O₄)₄(DMF)₈]_∞. Yield 7.5% (based on AgSPr)ⁱ)。

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.