CN114634627A - One-dimensional pyrazole mixed-valence copper fullerene coordination polymer and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of coordination polymers, and specifically discloses a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer and a preparation method and application thereof. The chemical formula of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer is {[Cu ₃ (C ₄ H ₂ N ₂ F ₃ ) ₃ ] ₂ [(μ ₃ -η ² :η ² :η ² ) ₂ - C ₆₀ ]Cl} _n , where: n is a non-zero natural number. The invention adopts the principle of self-assembly, directly utilizes the chemical activity of the C=C double bond on the surface of C ₆₀ , uses cuprous oxide as the copper source of monovalent cupric ions, and uses 4-trifluoromethyl-1H-pyrazole as an auxiliary One-dimensional pyrazole mixed-valence copper fullerene coordination polymer was synthesized by one-step solvothermal synthesis method using chlorobenzene as a solvent and the source of chlorine in the polymer with bridging ligand, sensitive temperature-induced conductivity change Responsive to changes in air-vacuum conductivity, and can be used as a material for the function of temperature and air-vacuum changes in electrical conductivity.

Description

One-dimensional pyrazole mixed valence copper fullerene coordination polymer and its preparation method and application

technical field

The invention belongs to the technical field of coordination polymers, and in particular relates to a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer and a preparation method and application thereof.

Background technique

Since the discovery of fullerene- _C60 in 1985, _C60 and its derivatives have been a research hotspot due to their unique structure and physicochemical properties, and many _C60 derivatives have been reported due to their applications in optics, magnetism, electrons, Potential applications in materials science fields such as catalysis and biology have been extensively studied. In recent years, C ₆₀ has achieved breakthrough results in the fields of light-emitting diodes, nonlinear optics, organic ferromagnets, superconductors, photovoltaic cells, nitrogen fixation, and interactions with biological targets. C ₆₀ complexes have unique physical and chemical properties, and the research on the electrochemical properties of C ₆₀ complexes enriches the development of conductor and semiconductor materials.

Conducting polymers are attractive electroactive materials in the field of organic electronics due to their tunable conductivity, and many efforts have been devoted to developing methods to improve the long-range order and crystallinity of conducting polymers, with the hope of maximizing polymer Delocalized carriers within the framework. Recent findings on the conductivity and mobility of conducting polymers have often linked the high crystallinity of the samples. There are very large delocalized conjugated π electrons on the surface of C ₆₀ , which can form a good carrier carrier. However, there are few studies on C ₆₀ polymers. These C ₆₀ polymers mainly use C ₆₀ externally derived groups to form derivatives. Then the polymerization reaction is carried out, which makes the operation steps cumbersome, the economic effect is low, and there is no stereotyped crystal structure. The research on C ₆₀ coordination polymers is even less, because the traditional preparation method of C ₆₀ complexes is relatively mild, and most of the obtained C 60 complexes are oligonuclear C ₆₀ complexes, so for C ₆₀ coordination polymers The nature of is poorly understood.

Therefore, there is an urgent need to develop a fullerene coordination polymer that has good thermal stability and can be recycled for many times to be used as a semiconductor material.

SUMMARY OF THE INVENTION

The present invention proposes a one-dimensional pyrazole mixed-valent copper fullerene coordination polymer and its preparation method and application, so as to solve one or more technical problems existing in the prior art, and at least provide a beneficial choice or creation condition.

In order to overcome the above technical problems, the present invention provides a one-dimensional pyrazole mixed valence copper fullerene coordination polymer and its preparation method and application. The azole mixed valence copper fullerene coordination polymer has a clear crystal structure, and is sensitive to temperature change and conductivity change and vacuum-air change.

The first aspect of the present invention is to provide a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.

Specifically, the chemical formula of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer is {[Cu ₃ (C ₄ H ₂ N ₂ F ₃ ) ₃ ] ₂ [(μ ₃ -η ² :η ² : η ² ) ₂ -C ₆₀ ]Cl} _n , wherein: n is a non-zero natural number, μ ₃ indicates that C ₆₀ is coordinated with 3 Cus, and η ² indicates that the coordination mode of Cu and C ₆₀ is one Cu and C ₆₀ A C=C double bond on the coordination.

As a further improvement of the above scheme, the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer is a trigonal crystal system, R-3m space group, and has a one-dimensional chain structure.

As a further improvement of the above scheme, the one-dimensional pyrazole mixed valence copper fullerene coordination polymer contains delocalized mixed valence copper complexes, specifically, in an average of every 6 Cu atoms, 5 Cu are +1 price, 1 Cu is +2 price.

The second aspect of the present invention provides a preparation method of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.

Specifically, the preparation method of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer comprises the following steps:

(1) get C ₆₀ and add in chlorine source solvent and mix, obtain mixture A;

(2) mixing copper source, 4-trifluoromethyl-1H-pyrazole and mixture A obtained in step (1) to obtain mixture B;

(3) heating the mixture B obtained in step (2), carrying out solvothermal reaction, and after cooling down, obtaining reactant C;

(4) washing and drying the reactant C obtained in step (3) to obtain the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer.

As a further improvement of the above scheme, the copper source is cuprous oxide, and the chlorine source solvent is a chlorobenzene solvent.

As a further improvement of the above scheme, the molar ratio of the C ₆₀ , the 4-trifluoromethyl-1H-pyrazole and the cuprous oxide is 1:(6-8):(2-3).

As a further improvement of the above scheme, the molar volume of the C ₆₀ in the chlorobenzene solvent is 0.008-0.01 mmol/mL.

As a further improvement of the above scheme, in step (1), ultrasonic waves are used for the mixing, and the mixing time is 10-30 minutes.

As a further improvement of the above scheme, in step (2), the temperature of the solvothermal reaction is 160-180° C., and the holding time is 48-72 hours.

As a further improvement of the above scheme, in step (2), the cooling system is to drop to room temperature at a rate of 2-5°C/h.

As a further improvement of the above scheme, steps (2) and (3) are both carried out under airtight conditions.

As a further improvement of the above scheme, in step (4), an aromatic solvent is used for the cleaning; preferably, the aromatic solvent is selected from at least one of benzene, toluene, p-xylene or chlorobenzene.

Specifically, the present invention adopts the chlorobenzene (boiling point of 131° C.) with a higher boiling point to react in a closed container as a solvent, and the reaction temperature is 160-180° C. The pressure inside the closed container due to high temperature is far greater than the normal 1 Atmospheric pressure, that is, the solvothermal reaction is carried out under the condition of high temperature and high pressure, and the crystalline coordination polymer prepared by this method has a definite crystal structure, high thermal stability and chemical stability.

At the same time, the present invention adopts the principle of self-assembly, directly utilizes the chemical activity of the C=C double bond on the surface of C ₆₀ , uses cuprous oxide as the copper source of monovalent cupric ions, and uses 4-trifluoromethyl-1H-pyrazole with 4-trifluoromethyl-1H-pyrazole One-dimensional pyrazole mixed-valence copper fullerene coordination polymers were synthesized by one-step solvothermal synthesis method using chlorobenzene as the auxiliary bridging ligand, using chlorobenzene as the solvent and the source of chlorine in the polymer. When the polymer is applied to semiconductor materials, it has a sensitive temperature-induced conductivity change response and an air-vacuum conductivity change response, and can be used as a material for the function of temperature and air-vacuum change-induced conductivity changes.

The third aspect of the present invention provides the application of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.

Specifically, the one-dimensional pyrazole mixed valence copper fullerene coordination polymer is used in semiconductor functional materials, temperature sensing devices or air sensing devices.

Compared with the prior art, the technical solution provided by the present invention has at least the following technical effects or advantages:

The invention realizes the rapid preparation of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer in single crystal form through a solvothermal synthesis method. The preparation method is fast, convenient, simple and cheap in raw materials, can be prepared in large quantities, and is beneficial to industrial production and application. The prepared one-dimensional pyrazole mixed-valence copper-fullerene coordination polymer can increase the conductivity of the complex by 4 orders of magnitude at room temperature and pressure compared with that in the vacuum state; The conductive current of the complexes can be increased by 3 orders of magnitude compared with that at 30 °C; and the conductivity of the complexes exhibits an exponential change with the temperature change. Therefore, it has a sensitive temperature-induced conductivity change response and an air-vacuum conductivity change response, and has good thermal stability, which can be used repeatedly for many times in semiconductor functional materials, temperature sensing devices and air sensing devices. There are good application prospects.

Description of drawings

Fig. 1 is the powder X-ray diffraction (PXRD) spectrum of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer of the embodiment of the present invention 1;

Fig. 2 is the Fourier transform infrared (FT-IR) spectrum of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer of the embodiment of the present invention 1;

Fig. 3 is the thermogravimetric analysis (TGA) spectrogram of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer of the embodiment of the present invention 1;

Fig. 4 is the solid-state ultraviolet-visible-near-infrared (UV-VIS-NIR) absorption spectrum of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of the embodiment of the present invention 1;

Fig. 5 is the coordination environment diagram of C ₆₀ molecule in the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of Example 1 of the present invention;

6 is a diagram of the coordination environment of 4-trifluoromethylpyrazole in the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of Example 1 of the present invention;

7 is a single chain structure diagram in the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of Example 1 of the present invention;

8 is a stacking diagram of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of Example 1 of the present invention along the a-axis direction;

9 is a stacking diagram of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of Example 1 of the present invention along the b-axis direction;

10 is a stacking diagram of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of Example 1 of the present invention along the c-axis direction;

11 is a Cu element X-ray photoelectron spectroscopy (XPS) test curve diagram of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of Example 1 of the present invention;

Fig. 12 is the silver electrode conductivity test chart of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer of Example 1 of the present invention;

Fig. 13 is the sample size chart of the conductivity test of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of Example 1 of the present invention;

Fig. 14 is the current-voltage (Current-Voltage) linear diagram under normal temperature and normal pressure of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer of Example 1 of the present invention;

Fig. 15 is the current-voltage contrast linear diagram of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in vacuum and normal pressure of Example 1 of the present invention;

16 is a temperature-variable current-voltage linear diagram of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of Example 1 of the present invention;

Fig. 17 is the odd-numbered variable temperature current-voltage linear diagram of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of Example 1 of the present invention;

18 is a temperature-conductivity fitting curve diagram of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of Example 1 of the present invention.

Detailed ways

The present invention will be specifically described below with reference to the embodiments, so as to facilitate the understanding of the present invention by those skilled in the art. It is necessary to point out that the embodiments are only used to further illustrate the present invention, and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art make non-essential improvements and The adjustment should still belong to the protection scope of the present invention. Meanwhile, the raw materials mentioned below are all commercially available products that are not described in detail; the process steps or preparation methods not mentioned in detail are the process steps or preparation methods known to those skilled in the art.

Example 1:

Synthesis of one-dimensional pyrazole mixed-valent copper fullerene coordination polymers:

Weigh 0.01 mmol C ₆₀ to dissolve it in 1 mL of chlorobenzene solution, sonicate for 10 min with a sonicator, then weigh 0.08 mmol 4-trifluoromethyl-1H-pyrazole, 0.03 mmol cuprous oxide and place it in 8 × In a 12mm rigid glass tube, add 1mL of chlorobenzene C ₆₀ solution with a concentration of 0.01mmol/mL after ultrasonic treatment. After ultrasonication, use a water welder (hydrogen-oxygen machine) to seal the glass tube orifice, and load it into stainless steel. In an iron box, heated to 180 °C in an oven, kept at a constant temperature for 72 h, then lowered to room temperature at a rate of 5 °C/h, filtered with open tube, cleaned with chlorobenzene, and dried naturally at room temperature to obtain a large number of black prisms The crystal like this is the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer (referred to as complex, the same below) of this example.

Obviously, the above-mentioned embodiments are only examples for clear description, and are not intended to limit the implementation manner. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. For example, the molar ratio of C ₆₀ , 4-trifluoromethyl-1H-pyrazole and cuprous oxide described in the present invention; the molar volume of C ₆₀ in chlorobenzene solvent; the temperature, holding time and cooling rate of solvothermal reaction ; One-dimensional pyrazole mixed valence copper fullerene coordination polymer with similar structure and effect to Example 1 can also be obtained. It is not necessary and impossible to list all the embodiments here, and the obvious changes or modifications derived therefrom still fall within the protection scope of the present invention.

Complex Characterization:

1. Crystal structure

The appropriate complex prepared in Example 1 was selected under an optical microscope and placed on a Rigaku XtaLAB (operating at 25kW power: 45kV, 40mA) single crystal diffractometer, using Cu Kα radiation (λ=1.5418) at ω/ Scan in theta mode and collect diffraction data at low temperature (100K). The structure was solved by a direct method (SHELXTL-2018), and F2 was refined using full-matrix least multiplication to obtain the coordinates and anisotropy parameters of all non-hydrogen atoms. The specific crystal data are shown in Table 1.

The complexes were basically characterized by powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) and ultraviolet-visible-near-infrared absorption spectroscopy (UV-Vis). The results are shown in Figures 1-4. FIG. 1 is a powder X-ray diffraction (PXRD) spectrum of the complex, and the ordinate Intensity in FIG. 1 represents the intensity. It can be seen from Figure 1 that the crystal phase of the complex is consistent with the simulated powder and has good crystal phase purity. Figure 1 is the X-ray diffraction pattern of the complex temperature-changing powder, which shows that these synthesized products exist in the form of crystals. The simulated powder is obtained by software simulation of the crystal structure data measured by single crystal diffraction, as shown in Figure 1. Each peak represents a crystal plane of the crystal structure. If the actual measured powder diffraction is in good agreement with the single crystal diffraction, it can be shown that the obtained material has good crystal phase purity and no other crystal phase. impurities. Figure 2 is the Fourier transform infrared (FT-IR) spectrum of the complex, wherein: the abscissa Wavenumbers represents the wave number; the ordinate Transmittance represents the transmittance. There are characteristic peaks of N=N and CF on C ₆₀ and 4-trifluoromethylpyrazole on the spectrum of Fig. 2, indicating that the complex has been synthesized. The relevant data of the complex crystal are shown in Table 1. Figure 3 is a thermogravimetric (TGA) analysis diagram of the complex, wherein: the abscissa Temperature represents the temperature; the ordinate Weight represents the weight. It can be seen from Figure 3 that the thermal stability of the complex can be stabilized at about 160 °C. Figure 4 is the solid ultraviolet-visible-near-infrared (UV-VIS-NIR) absorption spectrum of the complex, wherein: the abscissa Wavelength represents the wavelength; the ordinate Absorption represents the absorption. It can be seen from Figure 4 that the complex materials have strong absorption in the entire ultraviolet-visible-near-infrared region.

Table 1: {[Cu ₃ (C ₄ H ₂ N ₂ F ₃ ) ₃ ] ₂ [(μ ₃ -η ² :η ² :η ² ) ₂ -C ₆₀ ]Cl} _n Crystallographic Data

Note: ^a R ₁ =∑ _hkl (||F _o |-|F _c ||)/∑ _hkl |F _a |

As can be seen from Table 1, the chemical formula of the complex is {[Cu ₃ (C ₄ H ₂ N ₂ F ₃ ) ₃ ] ₂ [(μ ₃ -η ² :η ² :η ² ) ₂ -C ₆₀ ]Cl} _n , Among them, n is a non-zero natural number, and the material crystal belongs to the R-3m space group of the trigonal crystal system. Wherein, C ₄ H ₂ N ₂ F ₃ represents a deprotonated 4-trifluoromethylpyrazole anionic ligand.

The crystal structures of the complexes are shown in Figures 5-10. Wherein, Fig. 5 is the coordination environment diagram of C ₆₀ molecule in the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of the present invention (for the sake of clarity, the inventor has deleted the hydrogen atom and the guest chlorobenzene molecule); Fig. 6 is the coordination environment diagram of 4-trifluoromethylpyrazole in the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of the present invention (for the sake of clarity, the inventor has deleted the hydrogen atom and the guest chlorobenzene molecule) ; Fig. 7 is the single chain structure diagram of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer of the present invention (in order to show clearly, the inventor has deleted hydrogen atom, guest chlorobenzene molecule and 4-trifluoromethyl group trifluoromethyl group on pyrazole); Figure 8 is the stacking diagram of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of the present invention along the a-axis direction (for the sake of clarity, the inventor has deleted the hydrogen atom and guest chlorobenzene molecule); Figure 9 is a stacking diagram of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of the present invention along the b-axis direction (for the sake of clarity, the inventor has deleted the hydrogen atom and the guest molecule); FIG. 10 is a stacking diagram of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer of the present invention along the c-axis direction (for the sake of clarity, the inventors have deleted the hydrogen atom and the guest chlorobenzene molecule).

As can be seen from Fig. 5, the copper atoms take the form of tetracoordination, and each copper atom is coordinated with two Ns of 4-trifluoromethylpyrazole, then Cu-(η ² -(C=C)) The form of the bond is coordinated to _C60 , and the 4th coordination site is coordinated to the chlorine atom in the middle of the six 4-trifluoromethylpyrazole ligands (the chlorine atom is derived from the chlorobenzene solvent). Each _C60 molecule is coordinated with 6 Cu(I) atoms through 6 [6,6] bonds on two six-membered rings at opposite ends to form a hexanuclear fullerene copper coordination unit. 4-Trifluoromethylpyrazole bridges two of these hexanuclear fullerene copper coordination units via an N-Cu(I) coordination bond to form a one-dimensional copper hexanuclear fullerene pyrazole base unit Chain-like structure, there are chlorobenzene guest molecules in the gaps between the chains. . The chemical composition of the complex is {[Cu ₃ (C ₄ H ₂ N ₂ F ₃ ) ₃ ] ₂ [(μ ₃ -η ² :η ² :η ² ) ₂ -C ₆₀ ]Cl} _n , and its structure is characterized by 6 Cu atoms are bridged by 6 4-trifluoromethylpyrazoles and 1 Cl, so 6 Cu atoms need 7 positive charges to achieve charge balance, that is to say, for every 6 Cu atoms, on average, There are 5 Cu atoms with +1 valence and 1 Cu atom with +2 valence, so the complex is a typical delocalized mixed-valent copper complex.

2. Energy spectrum analysis

To further demonstrate the presence of mixed-valence copper atoms in the complexes, X-ray photoelectron spectroscopy (XPS) measurements were performed on the complexes. Figure 11 is the characteristic XPS spectrum of Cu element of the complex, wherein: the abscissa Binding Energy represents the binding energy. The sample shows two stronger peaks at 933.2 and 953.1 eV, corresponding to the 2p _3/2 and 2p _1/2 orbital peaks of copper, respectively. However, the orbital peak at 2p _3/2 of copper (933.2 eV) is stronger than the 2p ₃ / in common +2-valent copper compounds such as CuO (933.7 eV), CuCl ₂ (934.8 eV) and CuSO ₄ (934.9 eV) The ₂ orbital peaks are lower, but significantly higher than the 2p _3/2 orbital peaks in +1-valent copper compounds such as Cu ₂ O (932.5 eV) and CuCl (932.5 eV), indicating the charge valence near the Cu atom in the complex. Between +2 and +1 prices. There is also a broad satellite peak of Cu ⁺ in the range of 943.2-949.1 eV, indicating that there is copper in the +1 valence state in the complex. These analytical results are consistent with the delocalized mixed-valence nature of the complexes observed in the X-ray single crystal diffraction structure.

Performance Testing:

Conduct an experimental test on the conductive properties of the complex prepared in Example 1, Figure 12 is a schematic diagram of the silver electrode conductivity test of the complex, Figure 13 is a schematic diagram of the size of a single crystal of the complex's conductivity test, the measurement length is 0.05cm, and the horizontal The cross-sectional area is S=0.002×0.005=1×10 ⁻⁵ cm ² . The relevant test results and analysis results of the complexes are shown in Figures 14-18, wherein: Figure 14 is the current-voltage (Voltage-Current) linear diagram of the complexes tested at normal temperature and pressure (25°C, 101.325kPa), It can be seen that the current of the complex increases linearly with the increase of voltage.

The formula for calculating resistance is:

In this formula (1), R is the resistance of the object; U is the measured voltage of the object; I is the measured current of the object; by calculating the inverse of the slope of the straight line in Figure 14, the resistance of the complex at room temperature and pressure is 3.52×10 ⁹ Ω.

The formula for calculating conductivity is:

In this formula (2), ρ is the electrical conductivity of the object; l is the length of the object; S is the cross-sectional area of the object; R is the resistance of the object.

According to the size of the complex (length l=0.05cm, cross-sectional area S=1×10 ^-5 cm ² ), the conductivity is 4.70×10 ¹⁰ (S/cm), and the conductivity of the complex shows that the complex is in within the range of semiconductor materials. Figure 15 shows that the conduction current of the same complex decreases by 4 orders of magnitude at the same voltage when evacuated to 5×10 ^-5 Pa. During the vacuuming process, the macroscopic shape and state of the complex did not change; when the state of normal temperature and pressure was restored, the conductive current of the crystal was restored again. It can be seen that under vacuum, the complex is almost non-conductive and becomes a typical insulator. The conductivity of the complex at room temperature and pressure is increased by 4 orders of magnitude compared with that in the vacuum state, indicating that the conductivity of the complex changes with air. more sensitive.

Figure 16 is the current-voltage linear diagram of the complex at atmospheric pressure from 20°C to 150°C. It can be seen that the conductive current of the complex increases significantly at the same voltage as the ambient temperature increases. At the same time, as the ambient temperature increases, the current increases more and more at the same temperature increase interval. Figure 17 is a linear graph of the odd-numbered temperature-varying current-voltage of the complex. It can be seen from the figure that under the same voltage condition, the conduction current of the complex at 150°C increases by three orders of magnitude compared with that at 30°C. Fig. 18 is a fitting curve diagram of the reciprocal temperature-conductivity of the complex (fit degree R ² =0.999), and the additional content in the figure is the parameter value in the testing process. It can be seen from Figure 18 that the conductivity of the complex has a great influence on the temperature change, showing an exponential growth change, indicating that the conductivity of the complex is very sensitive to the temperature change.

The above test and analysis results show that the one-dimensional pyrazole mixed valence copper fullerene coordination polymer of the present invention has high thermal stability, and the electrical conductivity is very sensitive to air-vacuum changes and temperature changes. The copper valence fullerene coordination polymers have great application prospects in gas sensor and temperature control sensor materials.

Claims (10)

1. a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer, it is characterized in that, the chemical formula of described one-dimensional pyrazole mixed-valence copper fullerene coordination polymer is {[Cu ₃ (C ₄ H ₂ N ₂ F ₃ ) ₃ ] ₂ [(μ ₃ -n ² :n ² :n ² ) ₂ -C ₆₀ ]Cl} _n , where: n is a non-zero natural number, μ ₃ represents C ₆₀ and 3 Cu Coordination, η ² indicates that the coordination mode of Cu and C ₆₀ is that one Cu is coordinated to one C=C double bond on C ₆₀ . 2. the one-dimensional pyrazole mixed valence copper fullerene coordination polymer according to claim 1 is characterized in that, the one-dimensional pyrazole mixed valence copper fullerene coordination polymer is a trigonal crystal system, R -3m space group with a one-dimensional chain-like structure. 3. The one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to claim 1, wherein the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer contains delocalized mixed Valence copper complexes. 4. the preparation method of the one-dimensional pyrazole mixed valence copper fullerene coordination polymer described in any one of claim 1 to 3, is characterized in that, comprises the following steps: (1) get C ₆₀ and add in chlorine source solvent and mix, obtain mixture A; (2) mixing copper source, 4-trifluoromethyl-1H-pyrazole and mixture A obtained in step (1) to obtain mixture B; (3) heating the mixture B obtained in step (2), carrying out solvothermal reaction, and after cooling down, obtaining reactant C; (4) washing and drying the reactant C obtained in step (3) to obtain the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer. 5 . The one-dimensional pyrazole mixed-valent copper fullerene coordination polymer according to claim 4 , wherein the copper source is cuprous oxide, and the chlorine source solvent is a chlorobenzene solvent. 6 . 6. The one-dimensional pyrazole mixed-valent copper fullerene coordination polymer according to claim 5, wherein the C ₆₀ , the 4-trifluoromethyl-1H-pyrazole and the oxidized The molar ratio of cuprous was 1:(6-8):(2-3). 7. the preparation method of one-dimensional pyrazole mixed valence copper fullerene coordination polymer according to claim 5, is characterized in that, the molar volume of described C ₆₀ in described chlorobenzene solvent is 0.008-0.01mmol /mL. 8. the preparation method of one-dimensional pyrazole mixed-valent copper fullerene coordination polymer according to claim 4, is characterized in that, in step (3), the temperature of described solvothermal reaction is 160-180 ℃, The holding time is 48-72 hours. 9 . The preparation method of the one-dimensional pyrazole mixed-valent copper fullerene coordination polymer according to claim 4 , wherein steps (2) and (3) are both carried out under airtight conditions. 10 . 10. The application of the one-dimensional pyrazole mixed-valence copper-fullerene coordination polymer according to any one of claims 1 to 3 in semiconductor functional materials, temperature sensing devices or air sensing devices.

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