Organic-inorganic hybrid copper-based monomolecular crystal as well as preparation method and application thereof

Abstract

The invention discloses an organic-inorganic hybrid copper-based monomolecular crystal and a preparation method and application thereof, the molecular formula of the monomolecular crystal is (C9H7N) 2CuBr2, and the preparation method comprises the following steps: dissolving an organic cation source in a medium solvent to obtain an organic solution; dissolving a copper metal ligand in hydroiodic acid to obtain an acid solution; mixing the organic solution and the acid solution, putting the mixed solution into a sealed bottle filled with a diffusion solvent, sealing by a sealing cover to form a sealed system, keeping out of the light, standing after the diffusion solvent in the bottle is completely volatilized, and observing a light green needle-like crystal to obtain a finished product. Isoquinoline is selected as an organic cation source, copper bromide metal salt is selected as a metal ligand, the monomolecular crystal which is flexible in structure, small in molecular weight, high in stability and excellent in performance is prepared through an anti-solvent diffusion single crystal method, the synthesis process is simple, the preparation period is short, the yield is high, and environment friendliness is achieved; and the application of the monomolecular crystal in the field of multifunctional miniaturized circuits is widened.

Description

Technical Field

[0001] The invention belongs to the technical field of single molecule materials, and in particular relates to an organic-inorganic hybrid copper-based single molecule crystal and a preparation method and application thereof. Background Art

[0002] With the development of nanotechnology, molecular electronics and quantum effects, as a new type of single-molecule material with the advantages of cross-disciplinary development, it is a potential material in the field of next-generation integrated multifunctional miniaturized circuits. In the field of biosensing, high sensitivity, small portability and multifunctional biocompatibility are the standards for device evaluation, and the two magnetic states of the single-molecule spin crossover (SCO), which can be regulated by temperature, light, pressure, chemistry and magnetic field to form a low spin (LS) state and a high spin (HS) state, are ideal materials for preparing biologically usable devices.

[0003] At present, existing single-molecule materials mainly include organic molecules, metal-organic frameworks (MOFs) and polymers. Scientists have achieved their application in the field of biosensing by regulating and synthesizing groups with specific functions. For example, iron ions and fluorinated organic ligands are used as structural and functional units to develop a stimuli-responsive nanoagent, FIMOF-TA nanoparticles, for activatable 19F magnetic resonance imaging (MRI) and synergistic treatment of tumors (Nano Lett. 2023, 23, 11989-11998); for the regulation of single-molecule structures [Fe( 2Me L)(NCBH 3 ) 2 ](in: 2Me L=N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-

[0004] 1,2-ethanediamine), the emergence or suppression of thermally induced self-selected crossover behavior, and reversible switching responses have been demonstrated in organic-inorganic hybrid halides (J.Am.Chem.Soc.2023,145,9564-9570).

[0005] In addition, single-molecule electronics aims to develop new materials with high sensitivity, low power consumption and strong mechanical flexibility. Biosensing devices prepared from them have not only been successfully manufactured, but also show great potential in a series of applications, especially in molecular sensors, photodetectors, rectifiers, field-effect transistors and light-emitting diodes, as well as their integration in photovoltaic devices. However, most of the existing single-molecule materials, including organic molecules, MOFs, and polymers, do not have excellent thermal stability, which greatly limits the use of single-molecule devices. In addition, high-precision manufacturing and assembly of single-molecule structures are still complex, requiring control of the arrangement and properties of materials at the nanoscale, and the design and synthesis of new functionalized molecules and nanomaterials is not simple and requires a lot of experiments and optimization.

[0006] Although single-molecule materials have become an important part of the material family due to their advantages such as structural compatibility, flexibility and designability, single-molecule magnetic materials generally have low magnetic Curie temperatures, lack excellent stability, and have low melting points. It is urgent to design and synthesize new single-molecule complexes with high magnetic Curie temperatures. In the prior art, the synthesis method of single-molecule materials involves multi-step reactions, low yield of synthesized single molecules, and often accompanied by by-products. Specific reaction conditions and catalysts are required, and complex processes are required to obtain single-molecule materials with ideal functions. Summary of the invention

[0007] Based on this, the main purpose of the present invention is to provide an organic-inorganic hybrid copper-based single-molecule crystal, which has excellent thermal stability, compatibility, flexibility and an adjustable single crystal structure.

[0008] Another object of the present invention is to provide a method for preparing the organic-inorganic hybrid copper-based single-molecule crystal, selecting isoquinoline as an organic cation source and copper bromide metal salt as a metal ligand, and adopting an anti-solvent diffusion single crystal method to prepare a new type of single-molecule crystal with flexible structure, small molecular weight, high stability and excellent performance. The synthesis process is simple, the preparation cycle is short, the yield is high and it is environmentally friendly.

[0009] Another object of the present invention is to provide an application of the organic-inorganic hybrid copper-based single-molecule crystal in the preparation of a single-molecule photovoltaic device.

[0010] To achieve the above object, the present invention adopts the following technical solution:

[0011] In the first aspect of the present invention, there is provided an organic-inorganic hybrid copper-based single molecule crystal, which is prepared by an anti-solvent diffusion single crystal method using isoquinoline as an organic cation source and copper bromide metal salt as a metal ligand, and has a molecular formula of IQ 2 CuBr 2 , wherein IQ is isoquinolinyl, that is, the molecular formula is (C 9 H 7N) 2 CuBr 2 .

[0012] The second aspect of the present invention provides a method for preparing the organic-inorganic hybrid copper-based single-molecule crystal, using an anti-solvent diffusion single crystal method, comprising the following steps:

[0013] S1, dissolving an organic cation source in a medium solvent to obtain an organic solution;

[0014] S2, dissolving the copper metal ligand in hydroiodic acid to obtain an acid solution;

[0015] S3, mixing the organic solution and the acid solution to obtain a mixed solution;

[0016] S4, placing the mixed solution obtained in step S3 in a sealed bottle containing a diffusion solvent, sealing the bottle to form a closed system, and storing it away from light. After the diffusion solvent in the bottle has evaporated, let it stand until light green needle-shaped crystals are observed, thereby obtaining the organic cation source being isoquinoline and the copper metal ligand being copper bromide metal salt.

[0017] Preferably, in step S1, the medium solvent is dimethylformamide, and the molar volume ratio of isoquinoline to dimethylformamide is 2.5 mmol:3 mL.

[0018] Preferably, in step S2, the molar ratio of copper bromide to hydroiodic acid is 2 to 4:5.

[0019] Preferably, in step S4, the diffusion solvent is chloroform, and the volume thereof is the same as that of the medium solvent.

[0020] Furthermore, step S4 also includes the steps of separating, drying and collecting the light green needle-shaped crystals of the target product.

[0021] The third aspect of the present invention provides the use of the organic-inorganic hybrid copper-based single-molecule crystal in the preparation of a single-molecule photovoltaic device.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The present invention proposes an organic-inorganic hybrid copper-based single-molecule crystal, selects isoquinoline as an organic cation source, and copper bromide metal salt as a metal ligand. Through the easy coordination of nitrogen atoms and copper atoms of the two, which is derived from the lone pair electrons and electronegativity of nitrogen, and the metallic properties of copper and the ability to adapt to a variety of coordination environments, a new type of single-molecule crystal with flexible structure, small molecular weight, high stability and excellent performance is successfully prepared.

[0024] 2. The present invention uses the anti-solvent diffusion single crystal method, selects two easily coordinated isoquinoline organic ligands and copper bromide metal salts, and prepares organic-inorganic hybrid copper-based single molecule single crystals in large quantities. It has excellent thermal stability and innovative molecular structure, shows the potential for magnetic field regulation of ferromagnetism, and broadens the material selection of single molecule compounds in the field of multifunctional miniaturized circuits. It is a very promising single molecule single crystal with excellent performance that can be prepared on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 In the embodiment, IQ 2 CuBr 2 Single crystal XRD structure.

[0026] Figure 2 In the embodiment, IQ 2 CuBr 2 Crystal Explorer chemical energy intensity analysis diagram.

[0027] Figure 3 In the embodiment, IQ 2 CuBr 2 Thermogravimetric analysis diagram of . DETAILED DESCRIPTION

[0028] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several changes and improvements can also be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0029] Example 1

[0030] This embodiment adopts the anti-solvent diffusion single crystal method to prepare a copper isoquinoline-based single molecule single crystal, and the specific steps are as follows:

[0031] S1. Dissolve 2.5 mmol of isoquinoline in 3 mL of dimethylformamide to obtain an organic solution.

[0032] S2. Dissolve 1.5 mmol of copper bromide in 2.5 mmol of hydroiodic acid to obtain an acid solution.

[0033] S3. Mix the organic solution and the acid solution to obtain a black mixed solution.

[0034] S4, the prepared mixed solution was placed in a sealed large bottle containing 3 mL of chloroform, the lid was sealed to form a closed system, and the solution was stored away from light. After the chloroform in the large bottle was evaporated, light green needle-shaped crystals were observed after standing for 2 days. The target product was collected by separation and drying to obtain isoquinoline copper bromide single molecule single crystal IQ2 CuBr 2 .

[0035] At 223K, IQ 2 CuBr 2 The XRD test results of single crystal are as follows Figure 1 As shown, it can be seen that the single crystal is 21 / n It crystallizes in a monoclinic centrosymmetric space group, with unit cell parameters a=12.5220(3), b=4.0746(1), c=16.7791(4), α=γ=90°, β=100.308(1). During the synthesis process, its smallest asymmetric unit contains a structure with a copper atom as the center, a Cu-Br bond is formed between the coordination of bromide ions and copper ions, and the coordination bond of the complex isoquinoline is formed by the interaction between the lone pair of electrons of the nitrogen atom and the copper ion. The isoquinoline molecules are organized into flat layers on the ab plane dominated by van der Waals molecules, and the adjacent ab layers are staggered. The entire single molecule structure forms a dispersed individual, which increases the binding energy of the material and improves the crystal stability.

[0036] IQ 2 CuBr 2 Crystal Explorer chemical energy intensity analysis such as Figure 2 As shown, through the visualization calculation of the forces between atoms using Crystal Explorer, it can be seen that there is a strong force between H-Br bonds (red part), which enables multiple asymmetric single-molecule units to be gathered in the same unit cell.

[0037] IQ 2 CuBr 2 Thermogravimetric analysis of Figure 3 As shown, TG and DTG curves are used to describe IQ 2 CuBr 2 Thermogravimetric analysis showed that IQ 2 CuBr 2 The organic-inorganic hybrid single molecule starts to lose weight at about 102.2°C, and the organic isoquinoline starts to decompose at 165.9°C, indicating that the organic-inorganic hybrid metal halide prepared by the present invention has good thermal stability.

[0038] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An organic-inorganic hybrid copper-based single-molecule crystal, characterized in that: The product is prepared by an anti-solvent diffusion single crystal method using isoquinoline as an organic cation source and copper bromide as a metal ligand. The molecular formula is IQ2CuBr2, wherein IQ is an isoquinoline group, that is, the molecular formula is (C9H7N)2CuBr2.

2. The method for preparing the organic-inorganic hybrid copper-based single-molecule crystal according to claim 1, characterized in that: The method uses isoquinoline as an organic cation source and copper bromide as a copper metal ligand and adopts an anti-solvent diffusion single crystal method, comprising the following steps: S1, dissolving an organic cation source in a medium solvent to obtain an organic solution; S2, dissolving the copper metal ligand in hydroiodic acid to obtain an acid solution; S3, mixing the organic solution and the acid solution to obtain a mixed solution; S4. The mixed solution obtained in step S3 is placed in a sealed bottle containing a diffusion solvent, and the bottle is sealed to form a closed system. The solution is kept away from light, and the mixture is allowed to stand until the diffusion solvent in the bottle evaporates. Light green needle-shaped crystals are observed.

3. The method for preparing the organic-inorganic hybrid copper-based single-molecule crystal according to claim 1, characterized in that: In step S1, the medium solvent is dimethylformamide, and the molar volume ratio of isoquinoline to dimethylformamide is 2.5 mmol:3 mL.

4. The method for preparing the organic-inorganic hybrid copper-based single-molecule crystal according to claim 1, characterized in that: In step S2, the molar ratio of copper bromide to hydroiodic acid is 2-4:

5.

5. The method for preparing the organic-inorganic hybrid copper-based single-molecule crystal according to claim 1, characterized in that: In step S4, the diffusion solvent is chloroform, and the volume thereof is the same as that of the medium solvent.

6. The method for preparing the organic-inorganic hybrid copper-based single-molecule crystal according to claim 1, characterized in that: Step S4 also includes the steps of separating, drying and collecting the light green needle-shaped crystals of the target product.

7. Use of the organic-inorganic hybrid copper-based single-molecule crystal according to claim 1 in the preparation of single-molecule photovoltaic devices.

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