A high-nuclear copper fullerene complex, its preparation method and application

Abstract

This invention belongs to the field of carbon materials technology, and discloses a high-nuclear-core copper fullerene complex, its preparation method, and its applications. The chemical formula of this high-nuclear-core copper fullerene complex is 6(C7H). 10 N) + [Cu 30 Cl 36 (C 60 (C7H9N) 12 ] 6‑ ·3C7H9N. In this high-nuclearity copper fullerene complex, C 60 Provides a copper source with C=C double bonds, cuprous oxide as a monovalent copper ion, benzylamine, and Cl. ‑ To assist in coordination, high-nuclear copper fullerene complexes can absorb most of the near-infrared light, and the non-radiative transitions of the molecules are greater than the radiative transitions. They have high photothermal conversion efficiency and good electrical conductivity, as well as good photothermal stability, and can be recycled multiple times.

Description

Technical Field

[0001] This invention belongs to the field of carbon materials technology, and specifically relates to a high-nuclear copper fullerene complex, its preparation method, and its application. Background Technology

[0002] C 60 It is composed of 60 completely equivalent carbon atoms and has 30 carbon-carbon double bonds. Due to its unique molecular structure and electronic properties, it has potential applications in fields such as electrical conductivity and optoelectronics. However, research shows that very few carbon atoms... 60 Its derivatives can be used as conductive and photothermal materials.

[0003] Literature review indicates that photothermal functional materials with high near-infrared photothermal conversion efficiency possess two characteristics: 1. They absorb most of the near-infrared light; 2. Non-radiative molecular transitions are greater than radiative transitions. However, existing C... 60 In complex materials, the electron transition from the metal to the fullerene is restricted, resulting in poor photothermal conversion efficiency and generally poor electrical conductivity. Furthermore, most C... 60 Complexes are amorphous materials, and it is impossible to obtain a clear crystal structure, which is not conducive to studying the relationship between their structure and functional properties.

[0004] Therefore, there is an urgent need to provide a new C 60 The complex exhibits good photothermal conversion efficiency and, moreover, good electrical conductivity. Summary of the Invention

[0005] This invention aims to solve at least one of the technical problems existing in the prior art. To this end, this invention proposes a high-nuclear-core copper fullerene complex, its preparation method, and its applications. The high-nuclear-core copper fullerene complex of this invention can absorb most of the near-infrared light, and the non-radiative transitions of the molecule are greater than the radiative transitions, making it an ideal near-infrared photothermal conversion molecule. The high-nuclear-core copper fullerene complex of this invention, through π-electron coordination between the metal and the C=C bond, can significantly improve the absorption of visible light by the material, thereby improving the photothermal conversion efficiency. At the same time, functional materials with conductive properties require a linear or coplanar large conjugated system structure, which, under light or heating conditions, transitions conjugated π electrons to empty orbitals, thus exhibiting conductive properties. The high-nuclear-core copper fullerene complex also possesses this characteristic, making it an ideal conductive complex. Furthermore, the high-nuclear-core copper fullerene complex of this invention can be prepared through a relatively mild solvothermal reaction, and the high-nuclear-core copper fullerene complex has a well-defined crystal structure, high photothermal conversion efficiency, photothermal stability, and good ohmic contact.

[0006] A first aspect of the present invention provides a high-nuclear copper fullerene complex.

[0007] Specifically, a high-nuclear copper fullerene complex with the chemical formula 6(C7H) 10 N) + [Cu 30 Cl 36 (C 60 (C7H9N) 12 ] 6- ·3C7H9N.

[0008] Preferably, the crystal structure of the high-nuclear copper fullerene complex is trigonal. Space group.

[0009] Preferably, the photothermal conversion efficiency of the high-nuclear copper fullerene complex exceeds 80%; more preferably, the photothermal conversion efficiency of the high-nuclear copper fullerene complex is 85-87%, for example, as high as 86.75%.

[0010] Preferably, the conductivity of the high-nuclear copper fullerene complex is greater than 8 × 10⁻⁶. -10 S / cm; More preferably, the conductivity of the high-nuclear copper fullerene complex is (8-8.5)×10 -10 S / cm, for example, 8.46 × 10 -10 S / cm.

[0011] Preferably, the high-nuclear copper fullerene complex is in the form of black blocky crystals.

[0012] A second aspect of the present invention provides a method for preparing high-nuclear copper fullerene complexes.

[0013] Specifically, a method for preparing a high-nuclear-core copper fullerene complex includes the following steps:

[0014] (1) C 60 Dissolved in an organic solvent, solution A is obtained;

[0015] (2) Mix cuprous oxide, hydrochloric acid, benzylamine and solution A to obtain mixture B, then heat, keep warm and cool to obtain the high-nuclear copper fullerene complex.

[0016] Preferably, in step (1), the C 60 The ratio of the amount of organic solvent used is 0.001-0.01 mmol:1 mL, preferably 0.001-0.0015 mmol:1 mL.

[0017] Preferably, in step (1), the organic solvent includes at least one of benzene, chlorobenzene or toluene, with benzene being the preferred organic solvent.

[0018] Preferably, in step (1), ultrasound is used to promote the transfer of C 60 Soluble in organic solvents.

[0019] Preferably, the ultrasound duration is 5-20 minutes, more preferably 10-15 minutes.

[0020] Preferably, in step (1), under sealed conditions, ultrasound is used to promote the transfer of C... 60 Soluble in organic solvents.

[0021] Preferably, in step (2), the concentration of hydrochloric acid is 8-12 mol / L, more preferably 10-12 mol / L.

[0022] Preferably, in step (2), the cuprous oxide, hydrochloric acid, benzylamine, and C in solution A are... 60 The molar ratio is (5-30):(20-60):(5-30):1; more preferably, the cuprous oxide, hydrochloric acid, benzylamine and C in solution A are... 60 The molar ratio is (10-20):(30-40):(10-20):1.

[0023] Preferably, in step (2), the heating temperature is 55-105℃, more preferably 60-100℃.

[0024] Preferably, in step (2), the heating is carried out under sealed conditions.

[0025] Preferably, in step (2), the heat preservation is carried out at 55-105℃ for 60-75 hours, preferably 68-72 hours.

[0026] Preferably, in step (2), the cooling is performed at a rate of 2-6°C / h to room temperature, more preferably at a rate of 4-5°C / h. The room temperature is 25°C.

[0027] Preferably, in step (2), after cooling, the process also includes filtration, washing, and drying.

[0028] Preferably, the washing is performed using benzene.

[0029] Preferably, the drying is performed by natural air drying at room temperature.

[0030] This invention utilizes C through self-assembly 60 The high-nuclear-core copper fullerene complex was synthesized via a solvothermal one-pot method, using a C=C double bond, cuprous oxide as a monovalent copper ion source, and benzylamine and Cl- as auxiliary coordination ions. This high-nuclear-core copper fullerene complex can serve as a photothermal conversion and conductive material, exhibiting high photothermal conversion efficiency and good ohmic contact, and has potential applications in photothermal and conductive functional materials.

[0031] A third aspect of the present invention provides an application of a high-nucleus copper fullerene complex.

[0032] Specifically, a thermo-photoconversion material includes the aforementioned high-nuclear copper fullerene complex.

[0033] A conductive material comprising the aforementioned high-nuclear copper fullerene complex.

[0034] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0035] (1) In the high-nuclear copper fullerene complex of the present invention, C 60 Provides a copper source with C=C double bonds, cuprous oxide as a monovalent copper ion, benzylamine, and Cl. - To assist in coordination, the high-nuclear copper fullerene complex can absorb most of the near-infrared light, and the non-radiative transitions of the molecule are greater than the radiative transitions. It has high photothermal conversion efficiency and good electrical conductivity, as well as good photothermal stability, and can be recycled multiple times.

[0036] (2) This invention achieves rapid preparation of single-crystal high-nucleation copper fullerene complexes via a solvothermal one-pot method. This preparation method is rapid, convenient, and simple, with a yield exceeding 26%, for example, 26.5% (based on C). 60 Calculating yield is beneficial for industrial production and application. Attached Figure Description

[0037] Figure 1 This is the X-ray powder diffraction (PXRD) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention;

[0038] Figure 2 This is the Fourier transform infrared (FT-IR) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention;

[0039] Figure 3 This is the thermogravimetric analysis (TGA) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention;

[0040] Figure 4 This is the solid-state ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention;

[0041] Figure 5 This is a coordination environment diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention;

[0042] Figure 6 The C in the high-nuclear copper fullerene complex of Example 1 of this invention 60 @Cu 24 Core-shell structure diagram;

[0043] Figure 7 The C in the high-nuclear copper fullerene complex of Example 1 of this invention60 @Cu 30 @Cl 36 N 12 Diagram of a three-layered core-shell structure;

[0044] Figure 8 This is a schematic diagram of the photothermal experiment of the high-nuclear copper fullerene complex in Example 1 of the present invention;

[0045] Figure 9 This is a single photothermal conversion cycle diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention at 808 nm;

[0046] Figure 10 This is a cooling diagram of the high-nuclear copper fullerene complex after photothermal conversion in Example 1 of the present invention;

[0047] Figure 11 This is a Time-lnθ (time-temperature driven) graph of the cooling of the high-nuclear copper fullerene complex in Example 1 of the present invention;

[0048] Figure 12 This is a photothermal cycle diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention;

[0049] Figure 13 This is the current-voltage diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention. Detailed Implementation

[0050] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0051] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0052] Example 1: Preparation of high-nuclear copper fullerene complexes

[0053] A method for preparing a high-nuclear-core copper fullerene complex includes the following steps:

[0054] (1) Weigh 0.003 mmol C 60 Dissolve it in 3 mL of benzene, and sonicate for 10 minutes to obtain 0.001 mmol / L C. 60 Benzene solution (i.e., solution A);

[0055] (2) C 60The entire benzene solution was added to an 8*12 mm hard glass tube. Then, 0.05 mmol of cuprous oxide and 0.05 mmol of benzylamine were weighed. 8.5 μL of 12 mol / L hydrochloric acid (containing 0.102 mmol of pure HCl) was added to the hard glass tube and reacted with C. 60 The benzene solution was mixed to obtain mixture B. The mixture was then sealed in a hard glass tube using a hydrogen-oxygen generator, shaken thoroughly, and placed in an oven to be heated to 80°C and kept at that temperature for 72 hours. The mixture was then cooled to room temperature at a rate of 5°C / h. The hard glass tube was then removed, cut open with a glass cutter, and filtered. The mixture was washed with 1 mL of benzene, filtered again, and the resulting solid was collected and allowed to dry naturally at room temperature to obtain a large amount of black blocky crystals, which is the high-nuclear copper fullerene complex.

[0056] Example 2: Preparation of high-nuclear copper fullerene complexes

[0057] A method for preparing a high-nuclear-core copper fullerene complex includes the following steps:

[0058] (1) Weigh 0.0031 mmol C 60 Dissolve it in 3 mL of benzene, and sonicate it for 10 minutes to obtain C. 60 Benzene solution (i.e., solution A);

[0059] (2) C 60 The entire benzene solution was added to an 8*12 mm hard glass tube. Then, 0.05 mmol of cuprous oxide and 0.05 mmol of benzylamine were weighed, and 8.5 μL of 12 mol / L hydrochloric acid (containing 0.102 mmol of pure HCl) was added to the hard glass tube to react with C. 60 The benzene solution was mixed to obtain mixture B. The mixture was sealed in a hard glass tube using a hydrogen-oxygen generator, shaken thoroughly, and then heated to 80°C in an oven and kept at that temperature for 72 hours. The mixture was then cooled to room temperature at a rate of 5°C / h. The hard glass tube was then removed, cut open with a glass cutter, and filtered. The mixture was washed with 1 mL of benzene, filtered again, and the resulting solid was collected and allowed to dry naturally at room temperature to obtain a large amount of black blocky crystals, which is the high-nuclear copper fullerene complex (hereinafter referred to as the complex).

[0060] Product performance or effect test

[0061] 1. Structural characterization of high-nuclear copper fullerene complexes

[0062] The high-nuclear copper fullerene complex crystal prepared in Example 1 was taken under an optical microscope and placed on a Bruker D8 Venture single-crystal diffractometer (operating at 25kW power: 45kV, 40mA). Cu Kα radiation (λ = 1.5418) was used to scan in ω / θ mode, and diffraction data were collected at low temperature (100K). The structure was resolved by the direct method (SHELXTL-2018), and the F-matrix was analyzed using the full matrix least multiplication method. 2 The crystal was refined to obtain the coordinates and anisotropy parameters of all non-hydrogen atoms. Specific crystal data parameters are shown in Table 1.

[0063] Table 1: Crystallographic data of high-nuclear-core copper fullerene complexes

[0064]

[0065]

[0066] a R1=∑ hkl (||F o |-|F c ||) / ∑ hkl |F o |

[0067] As shown in Table 1, the chemical formula of the high-nuclear copper fullerene complex prepared in Example 1 is 6(C7H). 10 N) + [Cu 30 Cl 36 (C 60 (C7H9N) 12 ] 6- ·3C7H9N, the crystal belongs to the trigonal crystal system. Space group. Where C7H9N represents a benzylamine molecule, C7H... 10 N + This represents a protonated benzylamine cation.

[0068] The high-nuclear copper fullerene complex of Example 1 was characterized by X-ray powder diffraction (PXRD), Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), and ultraviolet-visible-near-infrared absorption spectroscopy (UV-Vis-NIR). The results are as follows: Figure 1-4 .

[0069] Figure 1 This is the X-ray powder diffraction (PXRD) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention; Figure 2 This is the Fourier transform infrared (FT-IR) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention; Figure 3This is the thermogravimetric analysis (TGA) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention; Figure 4 This is the solid-state ultraviolet-visible-near-infrared (UV-Vis-NIR) spectrum of the high-nuclear copper fullerene complex of Example 1 of the present invention.

[0070] Figure 1 The X-ray powder diffraction (PXRD) pattern of the high-nuclear copper fullerene complex of Example 1 is shown below. The measured PXRD pattern of the high-nuclear copper fullerene complex of Example 1 matches well with the PXRD pattern simulated by crystal structure, indicating that the complex has high crystal phase purity. Figure 1 The X-ray powder diffraction pattern shows that the synthesized products exist in crystalline form. The simulated values ​​are obtained through software simulation using crystal structure data measured by single-crystal diffraction. Figure 1 In the diagram, each peak represents a crystal plane of the crystal structure. If the actual measured powder diffraction matches the single-crystal diffraction, it indicates that the obtained product has good crystal phase purity and no other impurities.

[0071] Figure 2 The Fourier transform infrared (FT-IR) spectrum of the high-nuclear copper fullerene complex of Example 1 shows the presence of C. 60 The characteristic peaks of benzylamine indicate that the product is a high-nucleation copper fullerene complex.

[0072] Figure 3 The thermogravimetric (TG) analysis diagram of the high-nuclear copper fullerene complex in Example 1 shows that the high-nuclear copper fullerene complex can still exist stably when heated to about 100°C.

[0073] from Figure 4 It can be seen that the high-nuclear copper fullerene complex of Example 1 has strong absorption in the entire ultraviolet-visible-near-infrared region.

[0074] Figure 5 This is a coordination environment diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention; Figure 6 The C in the high-nuclear copper fullerene complex of Example 1 of this invention 60 @Cu 24 Core-shell structure diagram; Figure 7 The C in the high-nuclear copper fullerene complex of Example 1 of this invention 60 @Cu 30 @Cl 36 N 12 Diagram of a three-layered core-shell structure.

[0075] Figure 5 This is a coordination environment diagram of the high-nuclear copper fullerene complex of Example 1; Figure 6 It is the 30 Cu atoms in the high-nuclear copper fullerene complex at C 60The spatial distribution around the molecule forms a C 60 @Cu 30 Double core-shell structure; Figure 7 It is the C in high-nuclear copper fullerene complexes 60 @Cu 30 @Cl 36 N 12 The diagram of the three-layered core-shell structure shows that in C 60 @Cu 30 The spatial distribution of 36 Cl atoms and 12 N atoms on the outer edge of the double-layer structure forms a polyhedral layer with 48 vertices.

[0076] from Figure 5 It can be seen that the high-nuclearity copper fullerene complex is mainly composed of two parts, the main part being Cu. 24 Partially based on 8 Cu3 units, with the classic (μ3-η) 2 :η 2 :η 2 ) method bridging in C 60 On eight independent hexagons. Each Cu3 unit is further coordinated with three μ2-Cl atoms to form (μ2-Cl)3Cu3-[(μ3-η 2 :η 2 :η 2 [-hexagonal] unit. Furthermore, eight Cu3 units are linked together by 12 μ2-Cl atomic bridges, forming a 24-nuclear rhombic suboctahedron, similar to the rhombic suboctahedron C. 60 @Cu 24 The Cu3 units are coordinated via μ2-Cl. Therefore, each Cu(I) atom is coordinated with three Cl- anions and one C=C bond, completing the tetrahedral geometry of the Cu(I) atom. 60 The remaining six C=C bonds in the molecule are each coordinated with six independent Cu(I) atoms to form a C=C bond. 60 The structure of a saturated fullerene complex. Each of the six Cu(I) atoms is coordinated with two benzylamine molecules. The two N and two C atoms are almost coplanar with the Cu center, exhibiting a planar triangular Cu coordination pattern. The outermost layer of 36 Cl and 12 N atoms forms a third spherical shell with 48 vertices, enclosing the saturated fullerene C. 60 @Cu 30 (like Figure 7 ). Figure 6 and Figure 7 Based on Figure 5 Display after structural decomposition.

[0077] 2. Photothermal conversion test of high-nuclear copper fullerene complexes

[0078] The photothermal conversion experiment was conducted on the high-nuclear copper fullerene complex prepared in Example 1. The schematic diagram of the test is shown below. Figure 8 As shown, the relevant test results are as follows: Figure 9-12 As shown.

[0079] Figure 8 This is a schematic diagram of the photothermal experiment of the high-nuclear copper fullerene complex in Example 1 of the present invention; Figure 8 In this context, "sample" refers to a sample, "laser transmitter" refers to a laser transmitter, "IR thermal camera" refers to an infrared thermal imager, "Temperature" refers to temperature, and "quartz box" refers to a quartz cell.

[0080] Figure 9 This is a single photothermal conversion cycle diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention at 808 nm; Figure 10 This is a cooling diagram of the high-nuclear copper fullerene complex after photothermal conversion in Example 1 of the present invention.

[0081] Figure 11 This is a Time-lnθ (time-temperature driven) graph of the cooling of the high-nuclear copper fullerene complex in Example 1 of the present invention; Figure 11 In this context, "Time" represents time, "Linear fit" represents linear fitting, "Equation" indicates that the fitted equation is y = a + b*x with a fit of 0.99494, "Value" represents numerical value, and "Standard Error" represents standard error.

[0082] Figure 12 This is a photothermal cycle diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention.

[0083] Figure 9 The high-nuclear copper fullerene complex at 808 nm and power 0.650 W / cm 2 The single photothermal conversion cycle diagram (heating and cooling curves) under laser irradiation shows that the high-nuclear copper fullerene complex can reach a maximum temperature of 62.0℃ in 300s (after deducting the ambient temperature).

[0084] The formula for calculating photothermal conversion efficiency is:

[0085]

[0086] In this formula, η is the photothermal conversion efficiency; h is the heat transfer coefficient; S is the light-receiving area of ​​the sample in the quartz sample cell; ΔT max The difference between the highest temperature reached by the sample and the ambient temperature; I is the power of the irradiating laser; A 808The ultraviolet-visible absorbance of the complex at a laser wavelength of 808 nm is given.

[0087] In this formula, since the parameters h and S are often difficult to measure precisely, in experiments, another experimental formula for calculating the photothermal conversion efficiency is usually derived from this formula:

[0088]

[0089] In this formula, m i For the mass of the sample or quartz sample cell; C p,i τ is the specific heat capacity of the sample or quartz sample cell. s It is the Time-lnθ (time-temperature driven) curve. Figure 11 The slope of the linear fit is used to measure the heat transfer properties of the sample and the quartz sample cell.

[0090]

[0091] T represents the sample temperature measured during the natural cooling process over time T. sur For ambient temperature, T max This is the highest temperature reached by the sample under light.

[0092] In this invention example, the experimental data is: T sur =19℃, T max =62℃, I = 0.65W / cm 2 The mass m of the quartz sample cell 石 =1.25g, given the specific heat capacity C of quartz. p,石 =0.8J / (g·K), from Figure 10 The time-lnθ plot yields τ s = -118.0, absorbance A at 808 nm in solid-state UV-Vis absorption measurement 808 =0.48.

[0093] Mass m of the high-nuclear copper fullerene complex sample in Example 1 样 =0.05g. Specific heat capacity C of the sample. p,样 The Cc was obtained by measuring the average specific heat capacity of the samples in the range of 22°C to 62°C using a NETZSCH DSC 204F1 Phoenix differential scanning calorimeter (Germany) at a heating rate of 10°C / min. p,样 = 0.69 J / (g·K).

[0094] Substituting the above experimental data into the formula for calculating photothermal conversion efficiency, the calculation process for photothermal conversion efficiency is as follows:

[0095]

[0096] The photothermal conversion efficiency η of the high-nuclear copper fullerene complex in Example 1 was measured and calculated to be 86.75%.

[0097] Figure 12 The high-nuclear copper fullerene complex was obtained at 808 nm and a power of 0.650 W / cm. 2 The photothermal cycling diagram under laser irradiation shows that the high-nuclear copper fullerene complex exhibits good photothermal cycling stability. This indicates that the high-nuclear copper fullerene complex of this invention possesses high photothermal conversion efficiency and high photothermal stability for near-infrared light, and has potential applications in photothermal conversion materials.

[0098] 3. Experimental testing of the conductivity of high-nuclear copper fullerene complexes

[0099] The conductivity of the high-nuclear copper fullerene complex prepared in Example 1 was tested, and the results are as follows: Figure 13 As shown.

[0100] Figure 13 This is the current-voltage diagram of the high-nuclear copper fullerene complex of Example 1 of the present invention.

[0101] Figure 13 The test results of a high-nuclear copper fullerene complex sample with a diameter D of 3 mm and a thickness L of 0.52 mm under varying current and voltage conditions were obtained. The results were expressed as ρ = L / (RS) (where ρ is the conductivity of the sample; R is the resistance of the sample, which can be calculated from the current and voltage; and S is the cross-sectional area of ​​the sample, S = π(D / 2)). 2 Calculations show that the conductivity of the high-nuclear copper fullerene complex in Example 1 is 8.46 × 10⁻⁶. -10 S / cm, exhibiting good ohmic contact.

[0102] The above test and analysis results show that the high-nuclear copper fullerene complex of the present invention has high photothermal conversion efficiency, high photothermal stability, and an electrical conductivity of 8.46 × 10⁻⁶. -10 The S / cm ratio exhibits excellent ohmic contact. Therefore, high-nuclear copper fullerene complexes show great promise for applications in photothermal conversion and conductive functional materials.

[0103] If Cu in the high-nuclear copper fullerene complex of Example 1 of the present invention is replaced with Ag or Au, the complex with high photothermal conversion efficiency or good ohmic contact cannot be prepared.

Claims

1. A high-nuclear copper fullerene complex, characterized in that, 6(C7H 10 N) + [Cu 30 Cl 36 (C 60 )(C7H9N) 12 ] 6- ·3C7H9N; The high-nuclear copper fullerene complex is composed of [Cu 30 Cl 36 (C 60 (C7H9N) 12 ] 6- Composed of the rest; wherein [Cu 30 Cl 36 (C 60 (C7H9N) 12 ] 6- The structure is as follows: Cu 24 Partially based on 8 Cu3 units, with (μ3 η 2 :η 2 :η 2 ) method bridging in C 60 On 8 independent hexagons; each Cu3 unit is associated with three μ2 units. Cl atoms further coordinate to form (μ2) Cl)3Cu3 [(μ3 η2:η 2: η2) [Hexagonal] unit; 8 Cu3 units are composed of 12 μ2 Cl atoms are bridged together to form a 24-nuclear rhombic suboctahedron; in this 24-nuclear rhombic suboctahedron, each Cu(I) atom is connected to three Cl atoms. The anion coordinates with a C=C bond, completing the tetrahedral geometry of the Cu(I) atom; C 60 The remaining six C=C bonds in the molecule are each coordinated with six independent Cu(I) atoms to form a C=C bond. 60 The structure of the molecularly saturated fullerene complex is C60@Cu30; each of the six Cu(I) atoms is further coordinated with two benzylamine molecules. In the resulting ligand, the two N atoms and two C atoms are almost coplanar with the Cu center, presenting a planar triangular Cu coordination mode. The outermost 36 Cl - The C60@Cu30 is enclosed by a third spherical shell consisting of 12 N atoms arranged in a spherical structure with 48 vertices. The preparation method of the high-nuclear-core copper fullerene complex includes the following steps: (1) C 60 Dissolved in an organic solvent, solution A is obtained; (2) Mix cuprous oxide, hydrochloric acid, benzylamine and solution A to obtain mixture B, then heat, keep warm and cool to obtain the high-nuclear copper fullerene complex; In step (1), the C 60 The ratio of the amount of organic solvent used is 0.001-0.01 mmol: 1 mL; In step (2), the cuprous oxide, hydrochloric acid, and benzylamine react with C in solution A. 60 The molar ratio is (5-30):(20-60):(5-30):1; the heating temperature is 55-105 ℃; the heat preservation is performed at 55-105 ℃ for 60-75 hours.

2. The high-nuclear copper fullerene complex according to claim 1, characterized in that, The crystal structure of the high-nuclear copper fullerene complex is trigonal. Space group.

3. The high-nuclear copper fullerene complex according to claim 1, characterized in that, The photothermal conversion efficiency of the high-nuclear copper fullerene complex exceeds 80%.

4. The high-nuclear copper fullerene complex according to claim 1, characterized in that, The conductivity of the high-nuclear copper fullerene complex is greater than 8 × 10⁻⁶. -10 S / cm.

5. The high-nuclear copper fullerene complex according to claim 1, characterized in that, The high-nuclear copper fullerene complex is a black, blocky crystal.

6. A photothermal conversion material, characterized in that, Includes the high-nuclear copper fullerene complex according to any one of claims 1-5.

7. A conductive material, characterized in that, Includes the high-nuclear copper fullerene complex according to any one of claims 1-5.

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