Pentapyrazole fullerene copper complex as well as preparation method and application thereof

Abstract

The invention belongs to the field of carbon materials, and particularly discloses a pentapyrazole fullerene copper complex as well as a preparation method and application thereof. The chemical formula of the pentapyrazole fullerene copper complex is [CuC60 (Lpz) 5 (Lpy1)], [(CuC60 (Lpz) 5) 2 (Lpy2)] or [(CuC60 (Lpz) 5) 2 (Lpy3)], Lpz is 3-methyl-4-nitropyrazole, Lpy1 is 1, 2-bipyridine acetylene, Lpy2 is 4, 4-bipyridine, and Lpy3 is 1, 4-bipyridine-2, 5-dimethoxybenzene. C60 provides C = C double bonds, cuprous oxide serves as a copper source of cuprous ions, 3-methyl-4-nitropyrazole provides an addition site and assists in coordination with a ligand containing a pyridine group, and the prepared pentapyrazole fullerene copper complex has an obvious anti-saturated absorption response signal and shows a typical optical limiting effect. The non-linear transmittance is low, the third-order non-linear behavior is excellent, and the linear transmittance can exceed 70%. And the nonlinear transmittance is lower than 30%.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon materials, and in particular relates to a pentapyrazole fullerene copper complex and a preparation method and application thereof. Background Art

[0002] C 60 It is composed of 60 completely equivalent carbon atoms and has 30 carbon-carbon double bonds. Because of its unique molecular structure and electronic properties, it has potential applications in optoelectronics and other fields.

[0003] At present, third-order nonlinear optical materials have attracted more and more attention due to their potential applications in optical communications, optical data processing and storage, electro-optical devices and other fields. With the development of photonic and optoelectronic technologies, designing novel third-order nonlinear optical materials to meet the needs of various practical applications has become a hot issue. Among the many third-order nonlinear optical materials, organic materials have the following advantages compared to inorganic nonlinear optical materials: (1) huge and fast nonlinear response effects; (2) easy to process and easy to prepare into optical devices; (3) the nonlinear optical properties can be well regulated by chemical modification; (4) the goal of miniaturization of devices at the molecular level can be achieved. Most organic materials with strong nonlinear optical response are benzene rings or aromatic heterocyclic compounds, which have delocalized large π-electron systems. Because the large π-electron cloud distribution will produce a dipole moment under the irradiation of light waves, and the larger the dipole moment, the more significant the nonlinear effect. However, the existing C 60 Organic derivative molecules are often prone to dissociation and have the disadvantage of aggregation under high concentration conditions, leading to precipitation of solid products, which is not conducive to the study of their nonlinear effects.

[0004] Therefore, there is an urgent need to provide a new C 60 The complex has good nonlinear optical effects and has the potential to be an ideal optical limiting material. Summary of the Invention

[0005] The present invention aims to address at least one of the technical problems existing in the aforementioned prior art. To this end, the present invention provides a copper pentapyrazole fullerene complex, its preparation method, and its application. This copper pentapyrazole fullerene complex exhibits a distinct anti-saturation absorption response signal and a typical optical limiting effect, making it an ideal optical material with excellent third-order nonlinear optical effects.

[0006] The inventive concept of the present invention is as follows: The copper-pentapyrazole fullerene complex of the present invention combines organic molecules with metals through π-electron coordination between metals and C=C bonds to form a structurally ordered metal-organic complex, which can effectively prevent the decomposition and aggregation of organic molecules. At the same time, functional materials with strong nonlinear optical responses are mostly benzene ring or aromatic heterocyclic compounds. These compounds have a delocalized large π-electron system. This large π-electron cloud distribution generates a dipole moment under light wave irradiation, and the larger the dipole moment, the more significant the nonlinear effect. The copper-pentapyrazole fullerene complex of the present invention also has this characteristic, making it an ideal optical limiting material. Furthermore, the copper-pentapyrazole fullerene complex of the present invention can be prepared through a relatively mild solvothermal reaction, and the copper-pentapyrazole fullerene complex has a well-defined crystal structure, a distinct anti-saturation absorption response signal, and exhibits excellent third-order nonlinear optical effects, high linear transmittance, and low nonlinear transmittance.

[0007] In order to solve the above technical problems, the first aspect of the present invention provides a five-pyrazole fullerene copper complex, the chemical formula of the five-pyrazole fullerene copper complex is [CuC 60 (Lpz)5(Lpy1)]、[(CuC 60 (Lpz)5)2(Lpy2)] or [(CuC 60 (Lpz)5)2(Lpy3)], wherein: Lpz is 3-methyl-4-nitropyrazole, Lpy1 is 1,2-dipyridineacetylene, Lpy2 is 4,4-bipyridine, and Lpy3 is 1,4-dipyridine-2,5-dimethoxybenzene.

[0008] In some embodiments of the present invention, when the chemical formula of the pentapyrazole fullerene copper complex is [CuC 60 (Lpz)5(Lpy1)], namely [CuC 60 (C4H4N3O2)5(C 12 H8N2)], its crystal system is orthorhombic and its space group is Pbcm.

[0009] In some embodiments of the present invention, when the chemical formula of the pentapyrazole fullerene copper complex is [(CuC 60 (Lpz)5)2(Lpy2)], namely [(CuC 60 (C4H4N3O2)5)2(C 10 H8N2)]·4C6H5Cl, its crystal system is monoclinic and its space group is P21 / c.

[0010] In some embodiments of the present invention, when the chemical formula of the pentapyrazole fullerene copper complex is [(CuC 60 (Lpz)5)2(Lpy3)], namely [(CuC60 (C4H4N3O2)5)2(C 18 H 16 N2O2)]·4C6H5Cl, its crystal system is orthorhombic and its space group is Pbca.

[0011] In some embodiments of the present invention, the raw materials for preparing the copper pentapyrazole fullerene complex include C 60 , cuprous oxide, Lpz and a pyridine compound, wherein the pyridine compound is selected from any one of 1,2-dipyridyl acetylene, 4,4-bipyridine and 1,4-dipyridyl-2,5-dimethoxybenzene; the C 60 The molar ratio of , cuprous oxide, Lpz and pyridine compounds is 1:(1-20):(1-30):(1-20). Preferably, the C 60 , cuprous oxide, Lpz and Lpy have a molar ratio of 1:(1-10):(5-15):(1-10).

[0012] The second aspect of the present invention provides a method for preparing the above-mentioned pentapyrazole fullerene copper complex, comprising the following steps:

[0013] (1) C 60 Dissolve in an organic solvent to obtain solution A;

[0014] (2) mixing cuprous oxide, Lpz, and a pyridine compound with the solution A to obtain a solution B;

[0015] (3) heating the solution B to perform a solvothermal reaction to obtain the pentapyrazole fullerene copper complex.

[0016] Specifically, the present invention adopts the principle of self-assembly and utilizes C 60 A pentapyrazole fullerene copper complex was synthesized via a solvothermal one-pot method using a C=C double bond, cuprous oxide as a copper source for the monovalent copper ion, 3-methyl-4-nitropyrazole (Lpz) as an addition site, and a pyridine-containing ligand (i.e., a pyridine compound, Lpy) as an auxiliary coordination agent. This pentapyrazole fullerene copper complex can be used as a third-order nonlinear optical material, exhibiting low nonlinear transmittance and excellent third-order nonlinear behavior, and has the potential to be an ideal optical limiting material.

[0017] In some embodiments of the present invention, in step (1), the organic solvent is selected from at least one of benzene, chlorobenzene, and toluene; preferably chlorobenzene.

[0018] In some embodiments of the present invention, in step (1), the molar concentration of the solution A is 0.01-0.1 mol / L. Preferably, the molar concentration of the solution A is 0.01-0.015 mol / L.

[0019] In some embodiments of the present invention, in step (1), C 60 Ultrasonic treatment is used when dissolved in organic solvents to promote the 60 Soluble in organic solvents.

[0020] In some embodiments of the present invention, the ultrasonic treatment time is 5-20 minutes, preferably 10-15 minutes.

[0021] In some embodiments of the present invention, in step (3), the temperature of the solvent thermal reaction is 140-200°C; preferably 150-190°C.

[0022] In some embodiments of the present invention, in step (3), the solvent thermal reaction time is 60-75 hours; preferably 68-72 hours.

[0023] In some embodiments of the present invention, in step (3), a cooling step is further included after the solvothermal reaction, wherein the cooling step is performed at a rate of 2-6°C / hour to room temperature (25°C). Preferably, the cooling rate is 4-5°C / hour.

[0024] In some embodiments of the present invention, in step (3), the cooling further includes filtering, washing and drying steps.

[0025] In some embodiments of the present invention, the detergent used in the washing is chlorobenzene.

[0026] In some embodiments of the present invention, the drying is natural air drying at room temperature.

[0027] In some embodiments of the present invention, steps (1)-(3) are all performed under closed conditions.

[0028] The third aspect of the present invention provides the use of the above-mentioned pentapyrazole fullerene copper complex.

[0029] In some embodiments of the present invention, the application is application in third-order nonlinear optical materials, and the raw materials for preparing the third-order nonlinear optical materials include the above-mentioned pentapyrazole fullerene copper complex.

[0030] Compared with the prior art, the above technical solution of the present invention has at least the following technical effects or advantages:

[0031] (1) The copper pentapyrazole fullerene complex of the present invention is prepared by C 60The pentapyrazole fullerene copper complex provides a C=C double bond, cuprous oxide as a copper source for monovalent copper ions, 3-methyl-4-nitropyrazole as an addition site, and a ligand containing a pyridine group as an auxiliary coordination agent. The complex exhibits a distinct anti-saturation absorption response signal and a typical optical limiting effect, with low nonlinear transmittance and excellent third-order nonlinear behavior. It can achieve a linear transmittance exceeding 70%, for example, up to 72%, and a nonlinear transmittance below 30%, for example, as low as 26%.

[0032] (2) The present invention realizes the rapid preparation of single crystal pentapyrazole fullerene copper complex by a solvent thermal one-pot method. The preparation method is fast, convenient and simple, and the yield of pentapyrazole fullerene copper complex is 29.3-53.66% (based on C 60 calculation), which is beneficial to industrial production and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The X-ray powder diffraction spectrum of the copper pentapyrazole fullerene complex prepared in Example 1-3 of the present invention;

[0034] Figure 2 This is the Fourier transform infrared spectrum of the pentapyrazole fullerene copper complex prepared in Example 1-3 of the present invention;

[0035] Figure 3 This is the solid-state UV-visible spectrum of the pentapyrazole fullerene copper complex prepared in Examples 1-3 of the present invention;

[0036] Figure 4 [CuC 60 (Lpz)5] structure diagram;

[0037] Figure 5 This is a coordination environment diagram of the copper pentapyrazole fullerene complex prepared in Examples 1-3 of the present invention;

[0038] Figure 6 This is a schematic diagram of the structure of the third-order nonlinear optical test equipment;

[0039] Figure 7 Fullerene (C 60 ) Open aperture Z-scan curves at wavelengths of 532 nm and 1064 nm;

[0040] Figure 8 This is the open-pore Z-scan curve of the copper pentapyrazole fullerene complex prepared in Example 1 of the present invention at wavelengths of 532 nm and 1064 nm;

[0041] Figure 9This is the open-pore Z-scan curve of the copper pentapyrazole fullerene complex prepared in Example 2 of the present invention at wavelengths of 532 nm and 1064 nm;

[0042] Figure 10 This is the open-pore Z-scan curve of the copper pentapyrazole fullerene complex prepared in Example 3 of the present invention at wavelengths of 532 nm and 1064 nm;

[0043] Figure 11 This is a comparison of the open-pore Z-scan curves of the copper pentapyrazole fullerene complex and fullerene prepared in Examples 1-3 of the present invention at a wavelength of 532 nm.

[0044] Figure 12 This is a comparison of the open-pore Z-scan curves of the copper pentapyrazole fullerene complex and fullerene prepared in Examples 1-3 of the present invention at a wavelength of 1064 nm. DETAILED DESCRIPTION

[0045] The present invention is described in detail below with reference to the examples to facilitate understanding of the present invention by those skilled in the art. It is necessary to point out that the examples are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made to the present invention by those skilled in the art based on the above-mentioned invention should still fall within the scope of protection of the present invention. At the same time, the raw materials mentioned below that are not described in detail are all commercially available products; the process steps or preparation methods that are not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0046] Example 1

[0047] A copper pentapyrazole fullerene complex [CuC 60 (Lpz)5(Lpy1)], comprising the following steps:

[0048] (1) Weigh 0.011-0.015mmol C 60 It was dissolved in 1.1 mL of chlorobenzene and sonicated for 10 minutes to obtain 0.01 mmol / mL of C 60 Chlorobenzene solution, i.e., solution A;

[0049] (2) Solution A was added to an 8×12 mm hard glass tube, and 0.031 mmol of cuprous oxide, 0.088 mmol of 3-methyl-4-nitropyrazole, and 0.043 mmol of 1,2-dipyridyl acetylene (Lpy1) were weighed and added to the hard glass tube to mix with solution A to obtain mixture B;

[0050] (3) The hard glass tube was sealed with a hydrogen generator, shaken thoroughly, placed in an oven, heated to 180°C and kept warm for 72 hours, then cooled to room temperature (25°C) at a rate of 5°C / hour. The hard glass tube was then taken out, cut open with a glass cutter, filtered, and washed with 1 mL of chlorobenzene. After filtration, the solid obtained by filtration was taken and dried naturally at room temperature to obtain a large amount of black rod-shaped crystals, which were the copper pentapyrazole fullerene complex [CuC 60 (Lpz)5(Lpy1)].

[0051] Example 2

[0052] The only difference between Example 2 and Example 1 is that the 1,2-bipyridine acetylene (Lpy1) in step (2) is replaced by an equal amount of 4,4-bipyridine (Lpy2) to obtain a pentapyrazole fullerene copper complex [(CuC 60 (Lpz)5)2(Lpy2)].

[0053] Example 3

[0054] The only difference between Example 3 and Example 1 is that the 1,2-dipyridyl acetylene (Lpy1) in step (2) is replaced by an equal amount of 1,4-dipyridyl-2,5-dimethoxybenzene (Lpy3) to obtain a copper pentapyrazole fullerene complex [(CuC 60 (Lpz)5)2(Lpy3)].

[0055] Comparative Example 1

[0056] The only difference between Comparative Example 1 and Example 1 is that 3-methyl-4-nitropyrazole in step (2) was replaced with an equal amount of 3-nitropyrazole. The results showed that the expected black rod-shaped crystals could not be produced. This indicates that the reaction of 3-methyl-4-nitropyrazole with 1,2-dipyridylacetylene, 4,4-bipyridine, and 1,4-dipyridyl-2,5-dimethoxybenzene is specific. Other pyrazoles reacted with Lpy under the same conditions and failed to produce the corresponding pentapyrazole fullerene complex.

[0057] Structural characterization

[0058] 1. Crystal structure

[0059] The copper pentapyrazole fullerene complexes prepared in Examples 1-3 were taken under an optical microscope and placed on a Bruker D8 Venture single crystal diffractometer (operated at 25 kW power: 45 kV, 40 mA), using Cu Kα radiation (λ = 1.5418) in ω / θ mode scanning, and diffraction data were collected at low temperature (100 K). The structure was solved by a direct method (SHELXTL-2018), and the F was solved using the full matrix minimum multiplication method. 2Refinement was performed to obtain the coordinates and anisotropy parameters of all non-hydrogen atoms. Specific crystal data parameters are shown in Tables 1-3.

[0060] Table 1: Pentapyrazole fullerene copper complexes [CuC 60 Crystallographic data of [(Lpz)5(Lpy1)]

[0061]

[0062]

[0063]

[0064] Table 2: Pentapyrazole fullerene copper complexes [(CuC 60 Crystallographic data of (Lpz)5)2(Lpy2)]

[0065]

[0066]

[0067]

[0068] Table 3: Pentapyrazole fullerene copper complexes [(CuC 60 Crystallographic data of (Lpz)5)2(Lpy3)]

[0069]

[0070]

[0071]

[0072] As shown in Table 1-3, the chemical formula of the copper pentapyrazole fullerene complex prepared in Example 1-3 is [CuC 60 (Lpz)5(Lpy1)]、[(CuC 60 (Lpz)5)2(Lpy2)] or [(CuC 60 (Lpz)5)2(Lpy3)], where Lpz is 3-methyl-4-nitro, Lpy1 is 1,2-dipyridylacetylene, Lpy2 is 4,4-bipyridine, and Lpy3 is 1,4-dipyridyl-2,5-dimethoxybenzene. The three complexes described above exhibit orthorhombic, monoclinic, and orthorhombic space groups Pbcm, P21 / c, and Pbca, respectively.

[0073] The copper pentapyrazole fullerene complexes prepared in Examples 1-3 were characterized by X-ray powder diffraction (PXRD), Fourier transform infrared (FT-IR), and ultraviolet visible absorption spectroscopy (UV-Vis). Figure 1-3 .

[0074] Figure 1 -A. Figure 1 -B and Figure 1 -C correspond to the PXRD spectra of the copper pentapyrazole fullerene complex prepared in Examples 1-3. Figure 1 It can be seen that these complexes all exist in crystalline form, and the PXRD patterns of the complexes are in good agreement with the PXRD patterns obtained through crystal structure simulation, indicating that the complexes have high crystalline phase purity. The simulated value is obtained by software simulation of the crystal structure data measured by single crystal diffraction. Each peak represents a crystal plane of the crystal structure. If the actual measured powder diffraction pattern matches the single crystal diffraction pattern, it indicates that the obtained product has high crystalline phase purity and is free of other impurities.

[0075] Figure 2 -A. Figure 2 -B and Figure 2 -C correspond to the FT-IR spectra of the copper pentapyrazole fullerene complex prepared in Examples 1-3. Figure 2 It can be seen that there is C in the spectrum 60 The characteristic peaks of nitropyrazole and 1,2-dipyrazole indicate that the product is a pentapyrazole fullerene copper complex.

[0076] Figure 3 -A. Figure 3 -B and Figure 3 -C correspond to the UV-Vis spectra of the copper pentapyrazole fullerene complex prepared in Examples 1-3. Figure 3 It can be seen that the pentapyrazole fullerene copper complex has strong absorption in the entire ultraviolet-visible light region.

[0077] Figure 4 [CuC 60 (Lpz)5] structure diagram, which shows the position of the addition of the five pyrazole groups. Five 3-methyl-4-nitropyrazole molecules are on C 60 The spatial distribution on the molecule forms a C 60 There are five pyrazolyl addition structures.

[0078] Figure 5 -A. Figure 5 -B and Figure 5 -C correspond to the coordination environment diagrams of the copper pentapyrazole fullerene complexes prepared in Examples 1-3. Figure 4It can be seen that the five pyrazole ligands in the copper complex of pentapyrazole fullerene remove the H on NH and then add to the five C=C bonds around a five-membered ring of the fullerene molecule through the N atom, forming a new pentapyrazole fullerene (C 60 ) organic derivative, the five-membered ring is thus converted into a cyclopentadiene fragment, surrounded by five six-membered rings, and the cyclopentadiene is deprotonated to form a cyclopentadiene anion fragment. At this time, the Cu(I) with an empty orbital is four-coordinated with a carbon-carbon bond on the cyclopentadiene anion at η 2 The pyridine ligands coordinate with the copper pentapyrazoles in a coordinated manner, and with the nitrogen atoms of the two pyrazole groups to form a pentapyrazole copper fullerene molecular unit. This coordination unit then coordinates with copper through the nitrogen atoms of the pyridine ligands to form the corresponding three complexes.

[0079] Performance Testing

[0080] The three-order nonlinear optical test was performed on the copper pentapyrazole fullerene complex prepared in Examples 1-3. The schematic diagram of the open-aperture Z-scan test equipment is shown in FIG. Figure 6 The relevant test results are shown in Figure 7-12 shown.

[0081] The test process is as follows: the copper pentapyrazole fullerene complexes prepared in Examples 1-3 were uniformly dispersed in a polydimethylsiloxane (PDMS) matrix to form transparent and flexible films. The nonlinear optical and optical limiting behaviors of the samples were studied using a simple Z-scan device. The open-aperture Z-scan measurements were recorded with a pulse energy of 3-5 microjoules (μJ) under picosecond lasers at 532nm and 1064nm wavelengths and a repetition rate of 10Hz. 60 The same test was carried out to obtain experimental data for comparison.

[0082] Figure 7-10 Fullerene (C 60 ) and the open-pore Z-scan curves of the pentapyrazole fullerene copper complex prepared in Examples 1-3 at wavelengths of 532 nm and 1064 nm. Figure 11 The copper pentapyrazole fullerene complex and fullerene (C 60 ) Comparison of open-aperture Z-scan curves at 532 nm wavelength. Figure 12 The copper pentapyrazole fullerene complex and fullerene (C 60 ) Comparison of open-aperture Z-scan curves at 1064 nm wavelength. Figure 7-12 In the figure, the horizontal axis Z represents the sample position, and the vertical axis Normalized Transmittance represents the normalized transmittance.

[0083] Depend on Figure 7-12It can be seen that the Z-scan curves of the copper pentapyrazole fullerene complexes prepared in Examples 1-3 show obvious anti-saturation absorption response, showing a typical optical limiting effect, and the complexes show excellent third-order nonlinear behavior at both laser wavelengths, and are better than (C 60 ) has a stronger response signal. The test data shows that the copper pentapyrazole fullerene complex exhibits an anti-saturation absorption response when the pulse energy is 3μJ or greater. At a pulse energy of 5μJ, the test results are relatively stable, so the Z-scan curve test data at 5μJ was selected.

[0084] The results showed that fullerene (C 60 ), the copper pentapyrazole fullerene complexes prepared in Examples 1-3 have linear transmittances of 56%, 72%, 25% and 25% at a wavelength of 523 nm, and 71%, 57%, 48% and 36% at a wavelength of 1064 nm. Fullerene (C 60 ), the nonlinear transmittances of the copper-pentapyrazole fullerene complexes prepared in Examples 1-3 at a wavelength of 523 nm were 53%, 38%, 51% and 34% respectively; and at a wavelength of 1064 nm, the nonlinear transmittances were 52%, 26%, 48% and 54% respectively. That is, the lowest nonlinear transmittance of the copper-pentapyrazole fullerene complexes prepared in Examples 1-3 at a wavelength of 532 nm was 34%; and the lowest nonlinear transmittance at a wavelength of 1064 nm was 26%, which is much lower than that of the original fullerene (C 60 ) content of the same film transmittance. As a basic parameter for evaluating the performance of the optical limiting effect, Figure 7-12 The comparison of the curves and data shows that the copper-pentapyrazole fullerene complex prepared in Examples 1-3 not only has a high linear transmittance, up to 72%, but also has a high linear transmittance compared with the original fullerene (C 60 ), and has a lower nonlinear transmittance, which can be as low as 26%. This shows that the pentapyrazole fullerene copper complex prepared by the present invention has potential application value in third-order nonlinear optical materials and optical limiting materials.

[0085] For those skilled in the art to which the present invention belongs, a number of simple deductions or substitutions can be made without departing from the concept of the present invention, without having to resort to creative work. Therefore, based on the disclosure of the present invention, simple improvements made by those skilled in the art to the present invention should be within the scope of protection of the present invention. The above embodiments are preferred embodiments of the present invention, and all processes similar to the present invention and equivalent changes made should fall within the scope of protection of the present invention.

Claims

1. A copper pentapyrazole fullerene complex, characterized in that: The chemical formula of the copper pentapyrazole fullerene complex is [CuC 60 (Lpz)5(Lpy1)]、[(CuC 60 (Lpz)5)2(Lpy2)] or [(CuC 60 (Lpz)5)2(Lpy3)], wherein: Lpz is 3-methyl-4-nitropyrazole, Lpy1 is 1,2-dipyridineacetylene, Lpy2 is 4,4-bipyridine, and Lpy3 is 1,4-dipyridine-2,5-dimethoxybenzene.

2. The copper pentapyrazole fullerene complex according to claim 1, characterized in that When the chemical formula of the copper pentapyrazole fullerene complex is [CuC 60 (Lpz)5(Lpy1)], its crystal system is orthorhombic and its space group is Pbcm.

3. The copper pentapyrazole fullerene complex according to claim 1, wherein When the chemical formula of the copper pentapyrazole fullerene complex is [(CuC 60 (Lpz)5)2(Lpy2)], its crystal system is monoclinic and its space group is P21 / c.

4. The copper complex of pentapyrazole fullerene according to claim 1, characterized in that When the chemical formula of the copper pentapyrazole fullerene complex is [(CuC 60 (Lpz)5)2(Lpy3)], its crystal system is orthorhombic and its space group is Pbca.

5. The copper complex of pentapyrazole fullerene according to claim 1, characterized in that The copper pentapyrazole fullerene complex is a black rod-shaped crystal.

6. The copper complex of pentapyrazole fullerene according to claim 1, characterized in that The raw materials for preparing the copper pentapyrazole fullerene complex include C 60 , cuprous oxide, Lpz and a pyridine compound, wherein the pyridine compound is selected from any one of 1,2-dipyridyl acetylene, 4,4-bipyridine and 1,4-dipyridyl-2,5-dimethoxybenzene; the C 60 , cuprous oxide, Lpz and pyridine compounds have a molar ratio of 1:(1-20):(1-30):(1-20).

7. A method for preparing the copper pentapyrazole fullerene complex according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) C 60 Dissolve in an organic solvent to obtain solution A; (2) mixing cuprous oxide, Lpz, and a pyridine compound with the solution A to obtain a solution B; (3) heating the solution B to perform a solvothermal reaction to obtain the pentapyrazole fullerene copper complex.

8. The method for preparing a copper pentapyrazole fullerene complex according to claim 7, wherein: In step (1), the molar concentration of solution A is 0.01-0.1 mol / L.

9. The method for preparing a copper pentapyrazole fullerene complex according to claim 7, wherein: In step (3), the temperature of the solvent thermal reaction is 140-200° C.; and / or the time of the solvent thermal reaction is 60-75 hours.

10. A third-order nonlinear optical material, characterized in that: The raw materials for preparing the third-order nonlinear optical material include the pentapyrazole fullerene copper complex according to any one of claims 1 to 6.

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