A tetra-coordinated zinc-containing complex single crystal material, a preparation method and application thereof
By preparing single-crystal materials of four-coordinate zinc-containing complexes and combining self-assembly and X-ray diffraction techniques, the problem of deformation control of single-crystal materials of metal complexes was solved, achieving elastic bending and recovery under external force, simplifying the preparation process and increasing the yield.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HENAN UNIVERSITY
- Filing Date
- 2023-05-16
- Publication Date
- 2026-07-03
AI Technical Summary
Existing technologies struggle to effectively control the elastic and plastic mechanical deformation of single-crystal metal complexes, especially the intermolecular forces in complex three-dimensional structures are difficult to predict, resulting in fewer related reports.
Using a four-coordinate zinc-containing complex single crystal material, a one-step self-assembly synthesis strategy was adopted. By combining the four-coordinate tetrahedral configuration of the transition metal zinc ion with the strong intermolecular forces of 4-carbamoylpyridine, the order and deformability of the crystal lattice were unified, and the molecular structure was determined by X-ray single crystal diffraction.
This study achieved elastic bending and recovery of single-crystal materials under external force, providing a new approach to controlling the physical and chemical properties of flexible single-crystal materials, simplifying the preparation process, increasing yield, and clarifying the relationship between structure and bending performance.
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Figure CN116574115B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of flexible single-crystal material preparation technology, specifically relating to a four-coordinate zinc-containing complex single-crystal material, its preparation method, and its applications. The elastically bending single-crystal material can deform under external force and return to its original shape after the external force is removed, making it suitable for applications in wearable electronic devices and intelligent sensing. Background Technology
[0002] Flexible materials have significant application value in wearable devices, flexible optoelectronic devices, and intelligent sensing. Based on mechanical response type, flexibility can be divided into elastic deformation and plastic deformation. Organic polymers and metallic materials, as traditional flexible materials, have been extensively studied. In recent years, to further explore the structure-property relationship between material properties and structure, researchers have shown great interest in molecular-based flexible single-crystal materials. Molecular-based flexible single-crystal materials can organically unify the seemingly contradictory characteristics of lattice order and deformability, providing a method for revealing the microscopic mechanisms at the molecular level.
[0003] Currently, reported flexible single-crystal materials mainly focus on planar organic molecular materials with relatively simple molecular structures and relatively unified intermolecular forces. However, metal complexes often have tetrahedral or octahedral three-dimensional configurations, complex molecular stacking methods, and unpredictable intermolecular forces, so related reports are very rare. How to control the elastic and plastic mechanical deformation of metal complex single-crystal materials through reasonable molecular structure modification remains an important challenge in this field.
[0004] From a molecular structure perspective, during elastic deformation, molecular layer slippage is suppressed, molecules reorient, the outer lattice is stretched, and the inner lattice is compressed. Therefore, the elastic mechanical deformation of a single crystal is closely related to intermolecular forces. This invention provides an elastically bending single-crystal material, its preparation method, and its applications. By controlling the intermolecular forces in the lattice, the elastic and plastic deformation of the metal complex single-crystal material is achieved, thus realizing the regulation of the material's physical and chemical properties under the action of a force field. Summary of the Invention
[0005] The purpose of this invention is to provide a four-coordinate zinc-containing complex single crystal material, its preparation method and elastic properties, and to provide a new approach for developing flexible single crystal materials of metal complexes and for controlling the physical and chemical properties of single crystal materials under the action of a force field.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] A four-coordinate zinc-containing complex single-crystal material with the molecular formula [ZnL2(NCS)2](1, L = 4-carbamoylpyridine).
[0008] A method for preparing a single crystal material of a four-coordinate zinc-containing complex as described above, the method comprising the following steps:
[0009] 1) Dissolve NH4NCS and NH4NCS in 20 mL of ethanol and stir until homogeneous to obtain solution A;
[0010] 2) Add 4-carbamoylpyridine to solution A, stir for 30 minutes, and then filter.
[0011] 3) After the filtrate is left to stand for a week, colorless elongated crystals are obtained, which are the elastic bending single crystal materials.
[0012] Specifically, the molar ratio of Zn(ClO4)2·6H2O, NH4NCS and 4-carbamoylpyridine is 1:2:10.
[0013] Application of a tetracoordinate zinc-containing complex single crystal material as described above as an elastic material.
[0014] Experiments revealed that under external force, this four-coordinate zinc-containing complex single-crystal material can bend, and after the force is released, the single crystal returns to its original state. From a molecular structure perspective, during elastic bending, the outer lattice of the single crystal is stretched, while the inner lattice is compressed, which is closely related to the intermolecular forces within the lattice. Therefore, the bending properties of flexible single-crystal materials can be controlled by altering these intermolecular forces.
[0015] This invention provides a one-step self-assembly synthesis strategy for preparing a four-coordinate zinc-containing complex single-crystal material. By combining the four-coordinate tetrahedral configuration of the transition metal zinc ion with the strong intermolecular forces provided by the carbamoyl group in 4-carbamoylpyridine, the seemingly contradictory characteristics of lattice order and deformability are organically unified. Compared with traditional flexible single-crystal materials, this invention has the following advantages:
[0016] 1) This invention uses X-ray single-crystal diffraction technology to accurately determine the molecular structure of single-crystal materials containing four-coordinate zinc complexes;
[0017] 2) This invention adopts a one-step self-assembly synthesis strategy, which is simple in experimental steps, environmentally friendly, and yields high output.
[0018] 3) This invention introduces the transition metal zinc ion, providing a new approach for studying the elastic bending properties of tetrahedral single-crystal materials with four-coordinate tetrahedral configuration;
[0019] 4) This invention explores the influence of intermolecular forces on elastic bending, providing experimental basis and theoretical reference for regulating the elastic bending properties of single-crystal materials;
[0020] 5) Compared with traditional flexible materials, the mechanism relationship between the structure and bending properties of the target product of this invention is clearer. Attached Figure Description
[0021] Figure 1 This is the molecular structure of a single-crystal material containing a four-coordinate zinc complex. The four coordination sites of the zinc ion are occupied by two nitrogen atoms from the thiocyanate group and two nitrogen atoms from 4-carbamoylpyridine, thus the molecule exhibits a tetrahedral coordination configuration.
[0022] Figure 2 The shape of a single crystal sample of a four-coordinate zinc-containing complex;
[0023] Figure 3 This represents the molecular packing structure of a single-crystal material containing a four-coordinate zinc complex.
[0024] Figure 4 The intermolecular forces in single-crystal materials of four-coordinate zinc-containing complexes;
[0025] Figure 5 The process of elastic bending and recovery to the original state of single-crystal materials containing four-coordinate zinc complexes; Detailed Implementation
[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0027] The present invention will now be described in detail with reference to specific embodiments:
[0028] Example 1:
[0029] A four-coordinate zinc-containing complex single-crystal material with the molecular formula [ZnL2(NCS)2](1, L = 4-carbamoylpyridine).
[0030] A method for preparing a four-coordinate zinc-containing single-crystal material includes the following steps:
[0031] 1) Dissolve 0.037 g Zn(ClO4)2·6H2O (0.1 mmol) and 0.015 g NH4NCS (0.2 mmol) in 20 mL of ethanol solution and stir to dissolve;
[0032] 2) Add 0.1 mL of 4-carbamoylpyridine to the solution obtained in step 1);
[0033] 3) After stirring for 30 min, filter the reaction solution, let it stand to evaporate slowly, and after one week, colorless elongated crystals are obtained, which are the single crystal products of the four-coordinate zinc-containing complex.
[0034] Example 2:
[0035] A four-coordinate zinc-containing complex single-crystal material with the molecular formula [ZnL2(NCS)2](1, L = 4-carbamoylpyridine).
[0036] A method for preparing a four-coordinate zinc-containing single-crystal material includes the following steps:
[0037] 1) Dissolve 0.037 g Zn(ClO4)2·6H2O (0.1 mmol) and 0.015 g NH4NCS (0.2 mmol) in 20 mL of ethanol solution and stir to dissolve;
[0038] 2) Add 0.1 mL of 4-carbamoylpyridine to the solution obtained in step 1);
[0039] 3) After stirring for 30 min, filter the reaction solution, let it stand to evaporate slowly, and after one week, colorless elongated crystals are obtained, which are the single crystal products of the four-coordinate zinc-containing complex.
[0040] Select single-crystal samples of appropriately sized four-coordinate zinc-containing complexes and collect diffraction images using a single-crystal X-ray diffractometer (Rigaku Oxford XtaLAB PRO).
[0041] 1) Crystal plane indexing shows that the crystallographic c-axis is aligned with the long axis of the single-crystal material;
[0042] 2) The molecular skeleton was analyzed using a direct method. Non-hydrogen atoms were anisotropically refined using the SHELXL program and optimized using full-matrix least squares. Hydrogen atoms were added using a geometric hydrogenation method, and the molecular structure was refined using a riding mode.
[0043] 3) Molecular structure analysis revealed that two thiocyanate groups and two 4-carbamoylpyridine groups simultaneously coordinate with zinc ions to form a tetrahedral complex. Within the complex's lattice, strong N−H···O hydrogen bonds exist between the 4-carbamoyl groups, and the distance between the proton acceptor and proton donor of adjacent molecules is approximately 2.824 Å.
[0044] Example 3:
[0045] A four-coordinate zinc-containing complex single-crystal material with the molecular formula [ZnL2(NCS)2](1, L = 4-carbamoylpyridine).
[0046] A method for preparing a four-coordinate zinc-containing single-crystal material includes the following steps:
[0047] 1) Dissolve 0.037 g Zn(ClO4)2·6H2O (0.1 mmol) and 0.015 g NH4NCS (0.2 mmol) in 20 mL of ethanol solution and stir to dissolve;
[0048] 2) Add 0.1 mL of 4-carbamoylpyridine to the solution obtained in step 1);
[0049] 3) After stirring for 30 min, filter the reaction solution, let it stand to evaporate slowly, and after one week, colorless elongated crystals are obtained, which are the single crystal products of the four-coordinate zinc-containing complex.
[0050] The elastic properties of the single-crystal product of the four-coordinate zinc-containing complex were tested under a microscope. Under external force, the single-crystal material could bend, and after the external force was released, the single-crystal material returned to its initial state, and the results showed good repeatability.
[0051] The present invention uses X-ray single-crystal diffraction technology to determine the molecular structure of the four-coordinate zinc-containing complex single-crystal material prepared in Example 1 above.
[0052] The unit cell parameters before bending are as follows: orthorhombic crystal system. Fdd Space group 2, cell parameters a = 19.2123(10) Å, b = 36.518(2) Å, c = 5.3051(3) Å, α = 90°, β = 90°, γ = 90°, V = 3722.0(4) Å 3 Z = 4 R I = 0.0227 wR 2 = 0.0575. The cell parameters during bending are as follows: orthorhombic crystal system. Fdd Space group 2, cell parameters a = 19.144(3) Å, b = 36.459(7) Å, c = 5.2583(10) Å, α = 90°, β = 90°, γ = 90°, V = 3670.2(11) Å 3 Z = 8 R 1 = 0.0983 wR 2 = 0.2874.
[0053] Figure 1 This represents the molecular structure of a single-crystal material containing a four-coordinate zinc complex. (The structure is derived from...) Figure 1It can be seen that: the four-coordinate zinc-containing complex consists of 1 Zn 2+ Cation, 2 [NCS] − It consists of an anion and two 4-carbamoylpyridine molecules. The four coordination sites of the zinc ion are occupied by two nitrogen atoms from the thiocyanate group and two nitrogen atoms from the 4-carbamoylpyridine group, and the molecule exhibits a tetrahedral coordination configuration.
[0054] Figure 2 The shape of a single crystal sample of a four-coordinate zinc-containing complex. Figure 2 It can be seen that the four-coordinate zinc-containing complex is a colorless, elongated crystal, and its crystallographic c-axis is consistent with the long axis of the single crystal material.
[0055] Figure 3 This represents the molecular packing structure of a single-crystal material containing a four-coordinate zinc complex. Figure 3 It can be seen that the tetrahedral mononuclear molecules exhibit a one-dimensional structure with a "saddle"-shaped stacking arrangement through the π···π interaction between 4-carbamoylpyridines. This one-dimensional structure is further connected by NH···O hydrogen bonds to form a three-dimensional structure.
[0056] Figure 4 This refers to the intermolecular forces in single-crystal materials of four-coordinate zinc-containing complexes. Figure 4 It can be seen that there are strong NH···O hydrogen bond interactions within the four-coordinate zinc complex molecule;
[0057] Figure 5 This describes the elastic bending and recovery process of a four-coordinate zinc-containing single-crystal material. Figure 5 It can be seen that under the action of external force, the elongated single crystal of the four-coordinate zinc complex exhibits obvious bending behavior, and after the external force is released, the single crystal returns to its original shape.
[0058] This invention utilizes intermolecular forces to unify the lattice order and deformability of zinc-containing complex single-crystal materials, achieving elastic bending deformation of metal complex single-crystal materials. This provides a new approach for developing flexible single-crystal materials with three-dimensional configurations, and can be applied in fields such as flexible optoelectronic devices and wearable devices.
Claims
1. The application of a single crystal of a four-coordinate zinc-containing complex as an elastic material, characterized in that: The molecular formula of the single crystal material is [ZnL2(NCS)2] (L = 4-carbamoylpyridine); its preparation method includes the following steps: 1) Dissolve Zn(ClO4)2·6H2O and NH4NCS in 20 mL of ethanol and stir well to obtain solution A; 2) Add 4-carbamoylpyridine to solution A, stir for 30 minutes, and then filter. 3) After the filtrate is left to stand for a week, colorless elongated crystals are obtained, which are the elastic bending single crystal materials.