阅读说明：本技术 纳米土星型超分子材料及其制备方法和应用 (Nano star-shaped supermolecule material, preparation method and application thereof ) 是由 詹顺泽 李丹 李经鸿 李明德 张国辉 孙姗姗 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种纳米土星型超分子材料及其制备方法和应用。通过将2-甲基咪唑、富勒烯、芳香族化合物、三氟醋酸铜的氨水溶液混合后进行经过超声、加热、清洗和干燥后制得该纳米土星型超分子材料。本发明通过溶剂热方法一步合成纳米土星超分子材料,该制备方法快速、方便、简单且原料廉价,能够大量制备纳米土星型超分子配合物材料,有利于工业生产与应用。制得的纳米土星超分子材料具有较高的热稳定性,高效的光致电子转移功能,在光电材料方面具有巨大的应用前景。(The invention discloses a nano star-shaped supermolecule material and a preparation method and application thereof. The nano-star-shaped supermolecular material is prepared by mixing 2-methylimidazole, fullerene, aromatic compound and copper trifluoroacetate in ammonia water solution, and then performing ultrasonic treatment, heating, cleaning and drying. The nano star-earth supramolecular complex material is synthesized by a solvothermal method in one step, the preparation method is quick, convenient and simple, the raw materials are cheap, the nano star-earth supramolecular complex material can be prepared in a large scale, and the industrial production and application are facilitated. The prepared nano-grade Tuxing supermolecule material has higher thermal stability and high-efficiency photoinduced electron transfer function, and has huge application prospect in the aspect of photoelectric materials.)

1. A nano-class star-shaped supermolecular material features that its chemical formula is Cu₁₀(mim)₁₀·C₆₀Or Cu₁₀(mim)₁₀·C₇₀。

2. The nano-scale star-shaped supramolecular material as claimed in claim 1, wherein said Cu₁₀(mim)₁₀·C₆₀And the Cu₁₀(mim)₁₀·C₇₀All are triclinic, P-1 space group, C₆₀And C₇₀Respectively located in Cu by supramolecular action₁₀(mim)₁₀The center of the complex.

3. A method for preparing a nano-soil star-type supramolecular material as claimed in claim 1 or 2, characterized by comprising the following steps:

mixing 2-methylimidazole, fullerene, aromatic compound and copper trifluoroacetate in an ammonia water solution, and performing ultrasonic treatment to obtain a mixed solution A;

step two, heating the mixed solution A to 160-180 ℃, keeping the constant temperature for 48-72 hours, and cooling to room temperature at the speed of 3-5 ℃/hour to prepare a substance B;

step three, cleaning the substance B with ethanol, and then drying to obtain the nano-soil star-shaped supramolecular material;

the aromatic compound is one of toluene, p-xylene and chlorobenzene; the fullerene is C₆₀And C₇₀One kind of (1).

4. The preparation method according to claim 3, wherein the molar mass ratio of 2-methylimidazole, copper trifluoroacetate and fullerene is 10:10: 1; 3mL of the aromatic compound was added per 0.02mmol of fullerene.

5. The preparation method according to claim 3, wherein in the first step, the time of ultrasonic treatment is 10-30 min.

6. The method of claim 3, wherein the first and second steps are performed under closed conditions.

7. The method according to claim 3, wherein the drying in the third step is performed under vacuum.

8. The use of the nano-star-shaped supramolecular material as claimed in any one of claims 1-2 in photoelectric functional materials.

9. The use of the nano-star-shaped supramolecular material as claimed in any one of claims 1 to 2 in solar cell materials.

10. Use of the nano-star-shaped supramolecular material as claimed in any one of claims 1 to 2 in semiconductor materials of photosensitizers.

Technical Field

The invention relates to the field of supermolecule coordination chemistry, in particular to a nano star-shaped supermolecule material and a preparation method and application thereof.

Background

C₆₀The molecule is a spherical molecule having a diameter of about 0.7nm (Van der Waals diameter of about 1.0nm), C₇₀The molecule is an ellipsoid molecule with a short axis of about 0.712nm and a long axis of about 0.796nm, and both of the molecules as common fullerene have special spherical structural characteristics and electronic structural characteristics, and are good electron acceptors and energy acceptors. C₆₀And C₇₀As a guest (guest) molecule, a plurality of supermolecule systems can be constructed through the weak interaction of the sphere surface of the guest molecule and the surface of other host (host) molecules through non-covalent bonds. Under the stimulation of ultraviolet and visible light, the host and the guest in a supermolecular system often have the property of photoinduced energy/electron transfer, so that the supermolecular material is widely concerned in the aspects of photoelectric functional materials and solar cell materials.

The nano-meteor molecule is a supermolecular structure similar to meteor and peripheral aureole formed by surrounding fullerene guest molecule by nano-macrocyclic host molecule. However, no fullerene-embedded nano-meteor supramolecular material exists in the market at present, and the key point for preparing the nano-meteor supramolecular material is to prepare nano macrocyclic molecules at the periphery of a nano-meteor system. Such macrocyclic molecules are often formed by covalent bonding of 6-12 small molecules (primary starting materials), require preparation via multiple intermediates via a multistep organic synthesis process, and require complicated isolation and purification operations at each step, which severely affects the final overall yield.

Disclosure of Invention

The invention aims to solve the defects of the prior art and provides an embedded C₆₀The nanometer star-shaped supermolecule material and the preparation method.

In order to achieve the purpose, the invention adopts the following technical scheme:

provides a nano star-earth supramolecular material with a chemical formula of Cu₁₀(mim)₁₀·C₆₀Or Cu₁₀(mim)₁₀·C₇₀And mim is 2-methylimidazole. The Cu₁₀(mim)₁₀·C₆₀And the Cu₁₀(mim)₁₀·C₇₀All are triclinic, P-1 space group, C₆₀And C₇₀Respectively located in Cu by supramolecular action₁₀(mim)₁₀The center of the complex.

The invention also provides a preparation method of the nano star-shaped supermolecule material, which comprises the following steps:

mixing 2-methylimidazole, fullerene, aromatic compound and copper trifluoroacetate in an ammonia water solution, and performing ultrasonic treatment (ultrasonic treatment is performed to disperse the mixed solution) to obtain a mixed solution A;

step two, heating the mixed solution A to 160-180 ℃, keeping the constant temperature for 48-72 hours, and cooling to room temperature at the speed of 3-5 ℃/hour to prepare a substance B;

step three, cleaning the substance B with ethanol (washing off impurities on the surface of the substance B), and then drying to obtain the nano-star-shaped supermolecular material;

the aromatic compound is one of toluene, p-xylene and chlorobenzene; the fullerene is C₆₀And C₇₀One kind of (1).

Compared with solid phase reaction and synthesis reaction which is difficult to carry out, the performance of reactants is changed under solvothermal conditions, and the activity is improved, so that the self-assembly of the reactants is facilitated under the conditions to generate required substances. Under the solvothermal condition, the method is favorable for growing crystals with few defects and good orientation. The synthesized crystal has high crystallinity and easy control of the granularity of the product. 2-methylimidazole is easy to self-assemble with copper atom under solvothermal condition to form 2-methylimidazole copper complex, C₆₀And C₇₀Dissolved and dispersed in a solvent and easily used as a template agent to form embedded C with 2-methylimidazole copper complex through supermolecule acting force₆₀Or with an embedded C₇₀The supermolecule of the nanometer meteor.

Preferably, the molar mass ratio of the 2-methylimidazole to the copper trifluoroacetate to the fullerene is 10:10: 1; 3mL of the aromatic compound was added per 0.02mmol of fullerene.

Wherein in the first step, the ultrasonic treatment time is 10-30 min; the first step and the second step are carried out under a closed condition; the drying in step three is carried out under vacuum.

The nanometer star-shaped supermolecule material has huge application prospect in photoelectric functional materials, solar cell materials and semiconductor materials of photosensitizers.

The invention has the beneficial effects that: the nano star-earth supramolecular complex material is synthesized by a solvothermal method in one step, the preparation method is quick, convenient and simple, the raw materials are cheap, the nano star-earth supramolecular complex material can be prepared in a large scale, and the industrial production and application are facilitated. The prepared nano-grade Tuxing supermolecule material has higher thermal stability and high-efficiency photoinduced electron transfer function, and has huge application prospect in the aspect of photoelectric materials.

Drawings

FIG. 1 shows Cu₁₀(mim)₁₀·C₆₀PXRD spectrum of (1);

FIG. 2 shows Cu₁₀(mim)₁₀·C₆₀FT-IR spectrum of (1);

FIG. 3 shows Cu₁₀(mim)₁₀·C₆₀TGA profile of (a);

FIG. 4 shows Cu₁₀(mim)₁₀·C₆₀The structure of (1);

FIG. 5 shows Cu₁₀(mim)₁₀·C₆₀Solid state UV-vis spectrum of (a);

FIG. 6 shows Cu₁₀(mim)₁₀·C₆₀Tauc plot of complex;

FIG. 7 shows Cu₁₀(mim)₁₀·C₆₀Transient absorption spectrum of (a);

FIG. 8 shows Cu₁₀(mim)₁₀·C₇₀PXRD spectrum of (1);

FIG. 9 shows Cu₁₀(mim)₁₀·C₇₀FT-IR spectrum of (1);

FIG. 10 shows Cu₁₀(mim)₁₀·C₇₀TGA profile of (a);

FIG. 11 shows Cu₁₀(mim)₁₀·C₇₀The structure of (1);

FIG. 12 shows Cu₁₀(mim)₁₀·C₇₀Solid state UV-vis spectrum of (a);

FIG. 13 shows Cu₁₀(mim)₁₀·C₇₀Tauc plot of complex;

FIG. 14 shows Cu₁₀(mim)₁₀·C₇₀Transient absorption spectrum of (1).

Detailed Description

The concept and technical effects of the present invention will be clearly and completely described in the following embodiments to fully understand the objects, aspects and effects of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.