CN114634627B - One-dimensional pyrazole mixed-valence copper fullerene coordination polymer and preparation method and application thereof - Google Patents
One-dimensional pyrazole mixed-valence copper fullerene coordination polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN114634627B CN114634627B CN202210243796.8A CN202210243796A CN114634627B CN 114634627 B CN114634627 B CN 114634627B CN 202210243796 A CN202210243796 A CN 202210243796A CN 114634627 B CN114634627 B CN 114634627B
- Authority
- CN
- China
- Prior art keywords
- pyrazole
- dimensional
- fullerene
- mixed
- coordination polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention belongs to the technical field of coordination polymers, and particularly 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 valence 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. The invention adopts the self-assembly principle and directly utilizes C 60 The chemical activity of the C = C double bond on the surface, cuprous oxide is used as a copper source of monovalent copper ions, 4-trifluoromethyl-1H-pyrazole is used as an auxiliary bridging ligand, chlorobenzene is used as a solvent and a chlorine source in a polymer, and the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer is prepared by one-step synthesis through a solvothermal synthesis method, has sensitive response to the change of the electric conductivity caused by temperature and response to the change of the electric conductivity caused by air-vacuum, and can be used as a material with the function of the change of the electric conductivity caused by the change of the temperature and the air-vacuum.
Description
Technical Field
The invention belongs to the technical field of coordination polymers, and particularly relates to a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer and a preparation method and application thereof.
Background
The discovery of Fullerene-C since 1985 60 From then on, C 60 And the derivatives thereof are always the research focus due to the unique structure and physicochemical properties, and a plurality of C 60 Derivatives have been reported and have been studied in great numbers due to their potential applications in the fields of materials science, such as optics, magnetism, electronics, catalysis, and biology. In recent years, C 60 Research in the fields of light emitting diodes, nonlinear optics, organic ferromagnets, superconductors, photovoltaic cells, nitrogen fixation, interaction with biological targets, and the like has achieved breakthrough results. C 60 The complex has unique physical and chemical properties to C 60 The research on the electrochemical performance of the complex enriches the development of conductor and semiconductor materials.
Conducting electricityPolymers are attractive electroactive materials in the field of organic electronics because of their tunable electrical conductivity, and many efforts have been made to develop methods to improve the long-range order and crystallinity of conductive polymers in hopes of maximizing delocalized carriers within the polymer backbone. Recent efforts in terms of conductivity and mobility of conductive polymers often link together the high crystallinity of the sample. C 60 The surface has very large delocalized conjugated pi electrons, which can form good carrier carriers, but at present, the carrier has high carrier mobility 60 The study of the polymers is less, these C 60 Polymers mainly using C 60 The derivative is formed by externally connecting derivative groups, and then polymerization reaction is carried out, so that the operation steps are complicated, the economic effect is low, and no shaped crystal structure exists. And C is 60 Coordination polymers have been much less studied because of the traditional C 60 The preparation method of the complex is mild, and most of the obtained complex is oligonuclear C 60 Complex, therefore for C 60 The properties of coordination polymers are poorly understood.
Therefore, there is a need to develop a fullerene coordination polymer which has better thermal stability and can be recycled for use as a semiconductor material.
Disclosure of Invention
The invention provides a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer, and a preparation method and application thereof, which are used for solving one or more technical problems in the prior art and at least providing a beneficial selection or creation condition.
In order to overcome the technical problems, the invention provides a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer and a preparation method and application thereof.
The first aspect of the invention provides a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.
Specifically, the one-dimensional pyrazole mixed-valence copper fullerene complexThe chemical formula of the 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, mu 3 Is represented by C 60 Coordinated to 3 Cu, eta 2 Represents Cu and C 60 In a coordination mode of one Cu and C 60 One C = C double bond coordination above.
As a further improvement of the scheme, the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer is of a trigonal system, and an R-3m space group 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 a delocalized mixed-valence copper complex, specifically, 5 of Cu and 1 of Cu are respectively a +1 valence and a +2 valence, respectively, in 6 Cu atoms on average.
The second aspect of the 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-valence copper fullerene coordination polymer comprises the following steps:
(1) Get C 60 Adding the mixture into a chlorine source solvent, and mixing to obtain a mixture A;
(2) Mixing a copper source, 4-trifluoromethyl-1H-pyrazole and the mixture A prepared in the step (1) to obtain a mixture B;
(3) Heating the mixture B prepared in the step (2), carrying out a solvothermal reaction, and cooling to obtain a reactant C;
(4) And (4) cleaning and drying the reactant C prepared in the step (3) to obtain the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.
As a further improvement of the scheme, the copper source is cuprous oxide, and the chlorine source solvent is a chlorobenzene solvent.
As a further improvement of the above, said C 60 The molar ratio of the 4-trifluoromethyl-1H-pyrazole to the cuprous oxide is 1: (6-8): (2-3).
As the above-mentioned meansIn a further refinement of said 60 The molar volume in the chlorobenzene solvent is 0.008-0.01mmol/mL.
As a further improvement of the scheme, in the step (1), ultrasonic waves are adopted for mixing, and the mixing time is 10-30 minutes.
As a further improvement of the scheme, in the step (2), the temperature of the solvothermal reaction is 160-180 ℃, and the holding time is 48-72 hours.
As a further improvement of the scheme, in the step (2), the temperature reduction system is used for reducing the temperature to the room temperature at the speed of 2-5 ℃/h.
As a further improvement of the above scheme, both steps (2) and (3) are carried out under closed conditions.
As a further improvement of the above scheme, in the 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, chlorobenzene with a higher boiling point (the boiling point is 131 ℃) is used as a solvent for reaction in a closed container, the reaction temperature is 160-180 ℃, the pressure generated by high temperature in the closed container is far higher than normal 1 atmospheric pressure, namely, the solvothermal reaction is carried out under the conditions of high temperature and high pressure, and the crystalline coordination polymer prepared by the method has a definite crystal structure, and higher thermal stability and chemical stability.
Meanwhile, the invention adopts the self-assembly principle and directly utilizes C 60 The chemical activity of the C = C double bond on the surface, cuprous oxide is used as a copper source of univalent copper ions, 4-trifluoromethyl-1H-pyrazole is used as an auxiliary bridging ligand, chlorobenzene is used as a solvent and a chlorine source in a polymer, and the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer is prepared by one-step synthesis through a solvothermal synthesis method. When the polymer is applied to a semiconductor material, the polymer has sensitive temperature-induced conductivity change response and air-vacuum-induced conductivity change response, and can be used as a material in the aspect of the temperature and air-vacuum-induced conductivity change function.
The third aspect of the invention provides an application of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.
Specifically, the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer is applied to a semiconductor functional material, a temperature sensing device or an air sensing device.
Compared with the prior art, the technical scheme provided by the invention at least has the following technical effects or advantages:
the invention realizes the rapid preparation of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in a single crystal form by a solvothermal synthesis method, and the preparation method is rapid, convenient, simple, cheap in raw materials, capable of realizing mass preparation and beneficial to industrial production and application. The conductivity of the prepared one-dimensional pyrazole mixed-valence copper fullerene coordination polymer can be increased by 4 orders of magnitude at normal temperature and normal pressure compared with that of the coordination polymer in a vacuum state; under the same voltage condition, the conducting current of the complex at 150 ℃ can be increased by 3 orders of magnitude compared with that at 30 ℃; and the conductivity of the complex exhibits an exponential change with respect to temperature change. Therefore, the material has sensitive temperature-induced conductivity change response and air-vacuum-induced conductivity change response, has better thermal stability, can be recycled for multiple times, and has good application prospect in the aspects of semiconductor functional materials, temperature sensing devices, air sensing devices and the like.
Drawings
FIG. 1 is a powder X-ray diffraction (PXRD) spectrum of one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in example 1 of the present invention;
FIG. 2 is a Fourier transform infrared (FT-IR) spectrum of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to example 1 of the present invention;
FIG. 3 is a thermogravimetric analysis (TGA) spectrum of one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of example 1 of the present invention;
FIG. 4 is a solid state ultraviolet-visible-near infrared (UV-VIS-NIR) absorption spectrum of one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of example 1 of the present invention;
FIG. 5 shows C in the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in example 1 of the present invention 60 A coordination environment map of the molecule;
FIG. 6 is a diagram showing the coordination environment of 4-trifluoromethylpyrazole in the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in example 1 of the present invention;
FIG. 7 is a single-chain structure diagram of a one-dimensional pyrazole-valence copper fullerene coordination polymer in example 1 of the present invention;
FIG. 8 is a diagram showing a stacking of one-dimensional pyrazole-mixed-valence copper fullerene coordination polymers in example 1 of the present invention along the a-axis direction;
FIG. 9 is a diagram showing the stacking of one-dimensional pyrazole mixed-valence copper fullerene coordination polymers along the b-axis direction in example 1 of the present invention;
FIG. 10 is a diagram showing the stacking of one-dimensional pyrazole mixed-valence copper fullerene coordination polymers along the c-axis direction in example 1 of the present invention;
FIG. 11 is a Cu element X-ray photoelectron spectroscopy (XPS) test graph of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to example 1 of the present invention;
FIG. 12 is a graph showing the measurement of the conductivity of a silver electrode of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to example 1 of the present invention;
FIG. 13 is a dimensional chart of a sample for conducting capability test of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to example 1 of the present invention;
FIG. 14 is a Current-Voltage (Current-Voltage) line graph at room temperature and pressure for the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in example 1 of the present invention;
FIG. 15 is a current-voltage versus linear plot of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of example 1 of the present invention under vacuum and normal pressure;
FIG. 16 is a temperature swing current-voltage linearity plot for a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in accordance with example 1 of the present invention;
FIG. 17 is an odd-numbered temperature swing current-voltage line graph of one-dimensional pyrazole mixed-valence copper fullerene coordination polymer in accordance with example 1 of the present invention;
FIG. 18 is a temperature-conductivity fit plot of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to example 1 of the present invention.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercial products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to the person skilled in the art.
Example 1:
synthesis of one-dimensional pyrazole mixed-valence copper fullerene coordination polymer:
weigh 0.01mmol C 60 Dissolving in 1mL chlorobenzene solution, performing ultrasonic treatment for 10min by an ultrasonic instrument, weighing 0.08mmol 4-trifluoromethyl-1H-pyrazole and 0.03mmol cuprous oxide, placing in a 8X 12 mm rigid glass tube, and adding 1mL chlorobenzene C with concentration of 0.01mmol/mL after ultrasonic treatment 60 After the solution is subjected to ultrasonic treatment, a glass tube opening is sealed by a water welding machine (oxyhydrogen machine), the glass tube opening is filled into a stainless steel iron box, the glass tube opening is heated in an oven to 180 ℃ and then kept at a constant temperature for 72 hours, then the temperature is reduced to room temperature at a speed of 5 ℃/h, the glass tube opening is filtered, then the glass tube opening is cleaned by chlorobenzene, and natural drying is carried out at the room temperature to obtain a large number of black prismatic crystals, namely the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer (complex for short, the same below) of the embodiment.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. For example, C described in the present invention 60 4-trifluoromethyl-1H-pyrazole and cuprous oxide; c 60 Molar volume in chlorobenzene solvent; the temperature, the heat preservation time and the cooling rate of the solvothermal reaction; a one-dimensional pyrazole-mixed-valence copper fullerene coordination polymer having a similar structural effect to that of example 1 can also be obtained. It is not necessary or necessary to exhaustively enumerate all embodiments herein, and obvious variations therefromVariations or modifications are within the scope of the invention.
And (3) complex characterization:
1. crystal structure
The appropriate complex prepared in example 1 was taken under an optical microscope and placed on a Rigaku XtaLAB (run at 25kW power: 45kV, 40mA) single crystal diffractometer and scanned in an omega/theta fashion using Cu Ka radiation (λ = 1.5418) and diffraction data collected at low temperature (100K). The structure is analyzed by a direct method (SHELXTL-2018), and F2 is refined by using full matrix minimum multiplication to obtain coordinates and anisotropic parameters of all non-hydrogen atoms, and specific crystal data are shown in Table 1.
The complex is basically characterized by powder X-ray diffraction (PXRD), fourier transform infrared (FT-IR) and ultraviolet visible near infrared absorption spectrum (UV-Vis), and the results are shown in FIGS. 1-4, wherein FIG. 1 is the powder X-ray diffraction (PXRD) spectrum of the complex, and the ordinate Intensity in FIG. 1 represents the Intensity. As can be seen from FIG. 1, the crystal phase of the complex is consistent with that of the simulated powder, and the purity of the crystal phase is better. FIG. 1 is an X-ray diffraction diagram of temperature-changing complex powder, which illustrates that the synthesized products exist in the form of crystals, and simulated powder is obtained by simulating the crystal structure data measured by single crystal diffraction through software, wherein each peak represents a crystal face of the crystal structure in FIG. 1. FIG. 2 is a Fourier transform infrared (FT-IR) spectrum of the complex, wherein: the abscissa Wavenumbers represents the wavenumber; the ordinate transmittince represents the Transmittance. Presence of C on the map of FIG. 2 60 The characteristic peaks of N = N and C-F on 4-trifluoromethylpyrazole indicate that the complex has been synthesized, and the relevant data of the complex crystal are shown in Table 1. FIG. 3 is a Thermogravimetric (TGA) analysis of a complex wherein: the abscissa Temperature represents the Temperature; the ordinate Weight represents Weight. From FIG. 3, it can be seen that the thermal stability of the complex can be stabilized at about 160 ℃. FIG. 4 is a solid ultraviolet-visible-near infrared (UV-VIS-NIR) absorption spectrum of a complex wherein: horizontal axis levelength represents wavelength; the ordinate Absorption represents Absorption. As can be seen from FIG. 4, the complex material has strong absorption in the whole 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 ＝Σ hkl (||F o |-|F C ||)/Σ hkl |F o | 
as can be seen from Table 1, the complex has the formula { [ 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, and the material crystal belongs to a trigonal system R-3m space group. 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 FIGS. 5-10. Wherein, FIG. 5 shows C in the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to the present invention 60 A graph of the coordination environment of the molecule (for clarity, the inventors deleted the hydrogen atom and the guest chlorobenzene molecule); FIG. 6 is a diagram showing the coordination environment of 4-trifluoromethylpyrazole in the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer of the present invention (for clarity, the inventors deleted the hydrogen atom and the guest chlorobenzene molecule); FIG. 7 is a single chain structure diagram of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to the present invention (for clarity, the inventors have deleted the hydrogen atom, the guest chlorobenzene molecule, and the trifluoromethyl group on 4-trifluoromethylpyrazole); FIG. 8 is a one-dimensional pyrazole blend according to the present inventionStacking patterns of copper-valent fullerene coordination polymers along the a-axis direction (for clarity, the inventors deleted hydrogen atoms and guest chlorobenzene molecules); FIG. 9 is a packing diagram of a one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to the present invention along the b-axis direction (for clarity, the inventors have deleted hydrogen atoms and guest molecules); FIG. 10 is a stacking diagram of one-dimensional pyrazole-mixed-valence copper fullerene coordination polymers according to the present invention along the c-axis direction (for clarity, the inventors deleted hydrogen atoms and guest chlorobenzene molecules).
As can be seen from FIG. 5, the copper atoms take a tetracoordinated form, each copper atom being coordinated to the N of two 4-trifluoromethylpyrazoles and then by Cu- (. Eta. -. Eta.) (II) 2 Form of the- (C = C)) bond with C 60 Coordination, the 4 th coordination site forms a coordination with the chlorine atom located in the middle of the six 4-trifluoromethylpyrazole ligands (the chlorine atom originates from chlorobenzene solvents). Each C 60 The molecule passes through 6 of two six-membered rings at opposite ends [6,6 ]]The bond coordinates with 6 Cu (I) atoms to form a hexanuclear fullerene copper coordination unit. The 4-trifluoromethylpyrazole bridges two such hexanuclear fullerene copper coordination units through an N-Cu (I) coordination bond to form a one-dimensional chain structure with the hexanuclear fullerene pyrazolopyrite copper as a basic unit, and chlorobenzene guest molecules exist in gaps among 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 The structural feature is that 6 Cu atoms are bridged by 6 4-trifluoromethylpyrazoles and 1 Cl, so that 6 Cu atoms need 7 positive charges to achieve charge balance, that is, on average, 5 Cu atoms are +1 valent and 1 Cu atom is +2 valent in each 6 Cu atoms, so that the complex is a typical delocalized mixed-valence copper complex.
2. Energy spectrum analysis
To further demonstrate the presence of mixed-valence copper atoms in the complexes, X-ray photoelectron spectroscopy (XPS) testing was performed on the complexes. FIG. 11 is a Cu element characteristic XPS spectrum of a complex, wherein: the abscissa Binding Energy represents Binding Energy. The samples showed two comparisons at 933.2 and 953.1eVStrong peaks, corresponding to 2p of copper respectively 3/2 And 2p 1/2 Orbital peak. However, 2p of copper 3/2 But the orbital peak (933.2 eV) is more than the common + 2-valent copper compound such as CuO (933.7 eV), cuCl 2 (934.8 eV) and CuSO 4 2p in (934.9 eV) 3/2 Has a low orbital peak but is significantly higher than a +1 valent copper compound such as Cu 2 2p in O (932.5 eV) and CuCl (932.5 eV) 3/2 Orbital peaks, indicating that the charge valence near the Cu atom in the complex is between +2 and + 1. Cu is also present in the interval 943.2-949.1eV + The broad satellite peak of (a) indicates that copper in the +1 valence state is present in the complex. These analyses are consistent with the delocalized mixed-valence behavior of the complexes observed in X-ray single crystal diffraction structures.
And (4) performance testing:
the complex prepared in example 1 was subjected to experimental conductivity test, fig. 12 is a schematic diagram of conductivity test of silver electrode of the complex, fig. 13 is a schematic diagram of size of single crystal of the complex, the measured length is 0.05cm, and the cross-sectional area is S =0.002 × 0.005=1 × 10 -5 cm 2 . The results of the relevant tests and analyses for the complexes are shown in FIGS. 14-18, in which: FIG. 14 is a graph showing the Current-Voltage (Voltage-Current) linearity of the complex measured at normal temperature and pressure (25 ℃, 101.325 kPa), and it can be seen that the Current of the complex shows a linear increase with the increase of the Voltage.
The formula for calculating the resistance is:
in the formula (1), R is the resistance of the object; u is the object measurement voltage; i is object measurement current; the inverse of the slope of the straight line in FIG. 14 was calculated to obtain a complex having a resistance of 3.52X 10 at room temperature and pressure 9 Ω。
The conductivity is calculated as:
in the formula (2), ρ is the object conductivity; l is the length of the object; s is the cross-sectional area of the object; r is the object resistance.
According to the size of the complex (length l =0.05cm, cross-sectional area S = 1X 10) -5 cm 2 ) The conductivity was found to be 4.70X 10 10 (S/cm), the complex is within the range of semiconductor materials as can be seen from the conductivity of the complex. FIG. 15 shows the vacuum when it is pumped to 5X 10 -5 And when Pa is reached, the conducting current of the same complex under the same voltage is reduced by 4 orders of magnitude. In the process of vacuumizing, the macroscopic shape and state of the complex are not changed; when the normal temperature and normal pressure state is recovered again, the conductive current of the crystal is recovered again. It can be seen that under vacuum, the complex is almost non-conductive and becomes a typical insulator, and the conductivity of the complex increases by 4 orders of magnitude at normal temperature and normal pressure compared with that under vacuum, which indicates that the conductivity of the complex is sensitive to air change.
FIG. 16 is a current-voltage linear graph of the complex at 20 ℃ to 150 ℃ under normal pressure, and it can be seen that the conduction current of the complex at the same voltage is obviously increased along with the increase of the ambient temperature. Meanwhile, as the ambient temperature rises, the current increases more and more at the same temperature increase interval. FIG. 17 is a linear graph of odd-numbered temperature-variable current-voltage of the complex, and it can be seen that under the same voltage condition, the conduction current of the complex at 150 ℃ is increased by three orders of magnitude compared with that at 30 ℃. FIG. 18 is a plot of reciprocal temperature-Conductivity (Conductivity) fit (degree of fit R) for the complexes 2 = 0.999), the additional content in the figure is the parameter value during the test. From fig. 18, it can be seen that the conductivity of the complex has a large influence on the temperature change, and shows an exponential increase change, indicating that the conductivity of the complex is very sensitive to the temperature change.
The test and analysis results show that the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer has higher thermal stability, the conductivity is very sensitive to air-vacuum change and temperature change, and the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer has a larger application prospect in the aspects of gas sensors and temperature control sensor materials of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.
Claims (8)
1. A one-dimensional pyrazole mixed-valence copper fullerene coordination polymer is characterized in that the chemical formula of the one-dimensional pyrazole mixed-valence 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, mu 3 Is represented by C 60 Coordinated to 3 Cu, eta 2 Represents Cu and C 60 In a coordination manner of one Cu to C 60 One C = C double bond coordination on;
the preparation method of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer comprises the following steps:
(1) Get C 60 Adding the mixture into a chlorobenzene solvent for mixing to obtain a mixture A;
(2) Mixing cuprous oxide, 4-trifluoromethyl-1H-pyrazole and the mixture A prepared in the step (1) to obtain a mixture B;
(3) Heating the mixture B prepared in the step (2), carrying out a solvothermal reaction, and cooling to obtain a reactant C;
(4) And (4) cleaning and drying the reactant C prepared in the step (3) to obtain the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer.
2. 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 is a trigonal system, and the R-3m space group has a one-dimensional chain 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 a delocalized mixed-valence copper complex.
4. The one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to claim 1, wherein C is 60 The molar ratio of the 4-trifluoromethyl-1H-pyrazole to the cuprous oxide is 1: (6-8): (2-3).
5. The one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to claim 1, wherein C is 60 The molar volume in the chlorobenzene solvent is 0.008-0.01mmol/mL.
6. The one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to claim 1, wherein in the step (3), the temperature of the solvothermal reaction is 160-180 ℃, and the holding time is 48-72 hours.
7. The one-dimensional pyrazole mixed-valence copper fullerene coordination polymer according to claim 1, wherein the steps (2) and (3) are performed under a sealed condition.
8. Use of the one-dimensional pyrazole mixed-valence copper fullerene coordination polymer as claimed in any one of claims 1 to 7 in a semiconductor functional material, a temperature sensing device or an air sensing device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210243796.8A CN114634627B (en) | 2022-03-10 | 2022-03-10 | One-dimensional pyrazole mixed-valence copper fullerene coordination polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210243796.8A CN114634627B (en) | 2022-03-10 | 2022-03-10 | One-dimensional pyrazole mixed-valence copper fullerene coordination polymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114634627A CN114634627A (en) | 2022-06-17 |
| CN114634627B true CN114634627B (en) | 2023-02-28 |
Family
ID=81947973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210243796.8A Active CN114634627B (en) | 2022-03-10 | 2022-03-10 | One-dimensional pyrazole mixed-valence copper fullerene coordination polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114634627B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007123707A (en) * | 2005-10-31 | 2007-05-17 | Fujifilm Corp | Photoelectric conversion element, imaging element, and method for applying electrical field thereto |
| CN102088060A (en) * | 2010-12-06 | 2011-06-08 | 电子科技大学 | Laminated organic thin-film solar cell and preparation method thereof |
| JP2012014905A (en) * | 2010-06-30 | 2012-01-19 | Konica Minolta Holdings Inc | Organic electroluminescence element, illumination device, display device, and method of manufacturing organic electroluminescence element |
| CN110684202A (en) * | 2019-09-30 | 2020-01-14 | 汕头大学 | Two-dimensional layered imidazole copper C60Material, preparation method and application thereof |
| CN113444255A (en) * | 2021-05-28 | 2021-09-28 | 云南大学 | Imine covalent organic framework loaded fullerene C60Material, preparation method thereof and application of supercapacitor |
-
2022
- 2022-03-10 CN CN202210243796.8A patent/CN114634627B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007123707A (en) * | 2005-10-31 | 2007-05-17 | Fujifilm Corp | Photoelectric conversion element, imaging element, and method for applying electrical field thereto |
| JP2012014905A (en) * | 2010-06-30 | 2012-01-19 | Konica Minolta Holdings Inc | Organic electroluminescence element, illumination device, display device, and method of manufacturing organic electroluminescence element |
| CN102088060A (en) * | 2010-12-06 | 2011-06-08 | 电子科技大学 | Laminated organic thin-film solar cell and preparation method thereof |
| CN110684202A (en) * | 2019-09-30 | 2020-01-14 | 汕头大学 | Two-dimensional layered imidazole copper C60Material, preparation method and application thereof |
| CN113444255A (en) * | 2021-05-28 | 2021-09-28 | 云南大学 | Imine covalent organic framework loaded fullerene C60Material, preparation method thereof and application of supercapacitor |
Non-Patent Citations (2)
| Title |
|---|
| "Ultra-stable 2D cuprofullerene imidazolate polymer as a high-performance visible-light photodetector";Shunze Zhan et al.;《SCIENCE CHINA Materials》;20210115;第64卷(第6期);第1563-1569页 * |
| "咪唑功能化富勒烯衍生物作为反式三元聚合物太阳能电池的自组装阴极界面层";李丹等;《第四届新型太阳能电池学术研讨会》;20170528;第397页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114634627A (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Electrically conductive metal–organic frameworks | |
| Rosales et al. | Persistent dopants and phase segregation in organolead mixed-halide perovskites | |
| Kitagawa et al. | Charge Ordering with Lattice Distortions in a Conductive MMX-Chain Complex, Pt2 (d ta) 4I (d ta= CH3CS2-) | |
| Pop et al. | Chirality driven metallic versus semiconducting behavior in a complete series of radical cation salts based on dimethyl-ethylenedithio-tetrathiafulvalene (DM-EDT-TTF) | |
| Kobayashi et al. | Single-component molecular metals with extended-TTF dithiolate ligands | |
| Giorgi et al. | Cation role in structural and electronic properties of 3D organic–inorganic halide perovskites: A DFT analysis | |
| Liu et al. | Electrically conductive coordination polymers for electronic and optoelectronic device applications | |
| Horwitz et al. | Redox-active 1D coordination polymers of iron–sulfur clusters | |
| Kusamoto et al. | Zero-, one-and two-dimensional bis (dithiolato) metal complexes with unique physical and chemical properties | |
| Jin et al. | Exceptional electron conduction in two-dimensional covalent organic frameworks | |
| Odabaş et al. | Synthesis and electrochemical, in situ spectroelectrochemical, electrical and gas sensing properties of ball-type homo-and hetero-dinuclear phthalocyanines with four [1a, 8b-dihydronaphtho [b] naphthofuro [3, 2-d] furan-7, 10-diyl] bridges | |
| Gordillo et al. | The advent of electrically conducting double-helical metal–organic frameworks featuring butterfly-shaped electron-rich π-extended tetrathiafulvalene ligands | |
| Zasada et al. | Conjugated metal–organic macrocycles: synthesis, characterization, and electrical conductivity | |
| Bag et al. | Resonating valence bond and σ-charge density wave phases in a benzannulated phenalenyl radical | |
| Gupta et al. | Syntheses, crystal structures and conducting properties of new homoleptic copper (II) dithiocarbamate complexes | |
| Chen et al. | Dimensionality modulates electrical conductivity in compositionally constant one-, two-, and three-dimensional frameworks | |
| Yang et al. | Construction of monomers and chains assembled by 3d/4f metals and 4′-(4-carboxyphenyl)-2, 2′: 6′, 2 ″-terpyridine | |
| Shupp et al. | Synthesis and characterization of molybdenum (0) and tungsten (0) complexes of tetramethylthiourea: single-source precursors for MoS2 and WS2 | |
| Cordero et al. | Influence of temperature, pressure, and humidity on the stabilities and transition kinetics of the various polymorphs of FAPbI3 | |
| Payehghadr et al. | Preparation of cadmium (II) oxide nanoparticles from a new one-dimensional cadmium (II) coordination polymer precursor; spectroscopic and thermal analysis studies | |
| Kamakura et al. | Redox-Active Tin Metal–Organic Framework with a Thiolate-Based Ligand | |
| Wang et al. | Broad electronic modulation of two-dimensional metal–organic frameworks over four distinct redox states | |
| Yoon et al. | From N-to p-Type Material: Effect of Metal Ion on Charge Transport in Metal–Organic Materials | |
| Pal et al. | Phenalenyl-based neutral radical molecular conductors: Substituent effects on solid-state structures and properties | |
| Cai et al. | Multiple roles of 1, 4-diazabicyclo [2.2. 2] octane in the solvothermal synthesis of iodobismuthates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230524 Address after: 515063 Shantou University, Daxue Road, Shantou City, Guangdong Province Patentee after: SHANTOU University Patentee after: Jinan University Address before: 515063 Shantou University, Daxue Road, Shantou City, Guangdong Province Patentee before: SHANTOU University |