A solvent-induced complex material and its preparation method and application

Abstract

The present invention discloses a solvent-induced complex material, a preparation method and an application thereof, wherein the chemical formula of the complex material is [(1,2-bis(3-pyridyl)ethylene)(1,2,4,5-benzenetracarboxylate) 0.5 silver] n . The complex material of the present invention has a homogeneous polycrystalline structure, which is α-type and β-type respectively. α-type and β-type can be converted into each other in different solvents. Silver nitrate, 1,2-bis(3-pyridyl)ethylene and 1,2,4,5-benzenetetracarboxylic acid form an α-type complex through coordination self-assembly in a methanol solvent. The α-type complex is a one-dimensional chain structure. The α-type complex is dissolved in acetonitrile and recrystallized to form a β-type complex; the β-type complex is dissolved in methanol and recrystallized to reform the α-type complex. Compared with the α-type structure, the conductivity of the material with the β-type structure is increased by 58%. The synthesis method of the solvent-induced complex material of the present invention is simple, the synthesis conditions are mild, and the yield is high.

Description

Technical Field

[0001] The present invention belongs to the technical field of smart materials, and in particular relates to a solvent-induced complex material, a preparation method and an application thereof. Background Art

[0002] In chemical reactions, most reactions occur in solution. As a medium, the solvent has a significant influence on the reaction mechanism and kinetic parameters. Solvent effects arise from interactions between the solvent and the solute. In coordination chemistry, the solvent plays a significant role in the synthesis of complexes from organic ligands and metal salts via self-assembly reactions. Commonly used solvents in complex synthesis include water, nitriles, alcohols, amides, toluene, and other solvents of varying polarity. Due to the varying polarity and functional groups present in the solvent, interactions between the solvent and the initial reactants can occur, such as π-π interactions and hydrogen bonding. Furthermore, different solutes have varying physicochemical properties. When they react and crystallize in different solvents, even small differences in the solvent's molecular structure can lead to significant differences in the microstructure of the resulting complex. Therefore, using different solvents during complex preparation can induce structural changes, which in turn can alter the properties of the complex. Summary of the Invention

[0003] The present invention provides a solvent-induced complex material, a preparation method thereof, and an application thereof. The complex material of the present invention has a homogeneous polycrystalline structure, namely, α-type and β-type, and the α-type and β-type can be converted into each other in different solvents. The α-type complex is a one-dimensional chain structure. The α-type complex is dissolved in acetonitrile and then recrystallized to form a β-type complex; the β-type complex is dissolved in methanol and then recrystallized to reform the α-type complex. In the β-type structure, the distance between Ag...Ag in adjacent one-dimensional chains becomes shorter, resulting in a stronger metal-metal interaction. Compared with the α-type structure, the conductivity of the material with the β-type structure is increased by 58%. The synthesis method of the solvent-induced complex material of the present invention is simple, the synthesis conditions are mild, and the yield is high.

[0004] The complex material of the present invention is [(1,2-di(3-pyridyl)ethylene)(1,2,4,5-benzenetetracarboxylate) 0.5 silver] n , n is the number of repeating units, which is any positive integer. The structural formulas of the 1,2-di(3-pyridyl)ethylene unit and the 1,2,4,5-benzenetetracarboxylate unit are shown below:

[0005]

[0006] The complex material of the present invention has a homogeneous polycrystalline structure, which is α-type and β-type respectively. The α-type and β-type can be transformed into each other in different solvents.

[0007] The crystal of the α-type structure belongs to the triclinic crystal system, the space group is Pī, and the unit cell parameters are α=81.46(3)°, β=85.75(3)°, γ=72.75(3)°;

[0008] The β-type crystal belongs to the triclinic crystal system, the space group is Pī, and the unit cell parameters are α=109.97(3)°, β=100.71(3)°, γ=111.30(3)°.

[0009] The preparation method of the complex material of the present invention comprises the following steps:

[0010] Dissolve 1,2-di(3-pyridyl)ethylene, 1,2,4,5-benzenetetracarboxylic acid, and silver nitrate in a reactor, add methanol solvent, slowly stir to dissolve the reactants, and slowly evaporate the solvent at room temperature. After 3 days, colorless block crystals can be collected, which is the α-type structure complex.

[0011] Furthermore, the molar ratio of the 1,2-di(3-pyridyl)ethylene, 1,2,4,5-benzenetetracarboxylic acid, and silver nitrate is 1-2:1-2:1-2, preferably 2:1:2.

[0012] The collected blocky α-type crystals are ground and dissolved in acetonitrile solvent, and the solution is slowly evaporated at room temperature, filtered and washed to collect colorless long strip crystals, which are single crystals of the β-type complex.

[0013] The collected long strips of β-type crystals are ground and dissolved in methanol solvent, and the solution is slowly evaporated at room temperature, filtered and washed to collect colorless block crystals, which are single crystals of α-type complex.

[0014] That is, in acetonitrile and methanol solvents, the α-type and β-type structural complexes can be converted into each other.

[0015] The application of the complex material of the present invention realizes the transformation of different crystal forms of the complex material through different solvents, thereby realizing the regulation of the electrical conductivity of the material.

[0016] Furthermore, in acetonitrile solvent, the α-type is converted into the β-type structure, and the conductivity of the complex material is significantly improved.

[0017] Furthermore, in methanol solvent, the β-type is converted into the α-type structure, and the conductivity of the complex material decreases significantly.

[0018] Specifically, the conductivity of the α-structured complex material was found to be 30.5±1.4 S·cm -1 The conductivity of the β-structured complex material is 48.2±1.5S·cm -1 The conductivity of the β-type structure complex is increased by 58% compared with the α-type structure complex.

[0019] Furthermore, in the α-type structure, the [(1,2-di(3-pyridyl)ethylene)(1,2,4,5-benzenetetracarboxylate)] radical is formed, which continuously extends along the b-axis. 0.5 silver] n One-dimensional chain structure. Figure 1 As shown, two adjacent one-dimensional [(1,2-di(3-pyridyl)ethylene)(1,2,4,5-benzenetetracarboxylate) 0.5 silver] n The chains are connected to each other by hydrogen bonds to form a two-dimensional supramolecule ( Figure 2 ). The distance between Ag…Ag in two adjacent chains is In the β-type structure, the extension along the b-axis is also [(1,2-di(3-pyridyl)ethylene)(1,2,4,5-benzenetetracarboxylate) 0.5 silver] n The one-dimensional chain structure ( Figure 3 ), two adjacent one-dimensional chains are connected to each other through hydrogen bonds and weak interactions with Ag…O to form a two-dimensional supramolecular compound. Due to the weak interaction of Ag…O, the distance between Ag…Ag in the two adjacent chains is shortened, and the distance between Ag…Ag is A strong metal-metal interaction is formed. Due to the enhanced Ag…Ag interaction, the conductivity of the β-type structure is improved by 58% compared to the α-type structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a one-dimensional chain crystal structure diagram of the α-type structure;

[0021] Figure 2 This is a two-dimensional supramolecular crystal structure diagram of the α-type structure;

[0022] Figure 3 The topological structure diagram of the two-dimensional supramolecular with α-type structure;

[0023] Figure 4 This is a one-dimensional chain crystal structure diagram of the β-type structure;

[0024] Figure 5 This is a two-dimensional supramolecular crystal structure diagram of the β-type structure;

[0025] Figure 6 The topological structure diagram of the two-dimensional supramolecule with β-type structure;

[0026] Figure 7 This is the three-dimensional supramolecular structure diagram of the β-type structure;

[0027] Figure 8 This is the three-dimensional supramolecular topological structure diagram of the β-type structure. DETAILED DESCRIPTION

[0028] Non-limiting examples are described below:

[0029] 1. Preparation of α-type structural complexes

[0030] Place 1.82g (10mmol) of 1,2-di(3-pyridyl)ethylene, 1.27g (5mmol) of 1,2,4,5-benzenetetracarboxylic acid, and 1.70g (10mmol) of silver nitrate in a small beaker. Add 100mL of methanol to the beaker and place the beaker on a magnetic stirrer to slowly stir until the sample is completely dissolved. Place the beaker in a fume hood and evaporate the solvent at room temperature. After 3 days, colorless block crystals will be obtained. Filter and collect the crystals, and dry them at room temperature to obtain an α-type structural complex with a yield of 2.70g and a yield of 65%. Its crystallographic parameters are as follows:

[0031] Crystallographic parameters of α-type structural complexes: C 17 H 12 N2O4Ag,M r =416.16,triclinic,space groupPī, α=81.46(3)°, β=85.75(3)°, γ=72.75(3)°, Z=2,D c =1.867g·cm -3 ,μ=1.386mm -1 ,13849reflectionsmeasured,3391unique reflections(R int =0.0194), 3121 observed reflections (I>2σ(I), 217 parameters, R1 = 0.0269, wR2 = 0.0682, S = 1.078.

[0032] Figure 1 This is a one-dimensional chain crystal structure diagram of the α-type structure;

[0033] Figure 2 This is a two-dimensional supramolecular crystal structure diagram of the α-type structure;

[0034] Figure 3This is the topological structure diagram of the two-dimensional supramolecule with α-type structure.

[0035] 2. Conversion of α-type structural complexes to β-type structural complexes

[0036] Grind 1g of a single crystal of the α-form complex into a powder and place it in a small beaker. Add 50mL of acetonitrile to dissolve the α-form complex completely. Place the beaker in a fume hood and allow the solvent to evaporate at room temperature. After two days, colorless, elongated crystals will be obtained. Filter, collect the crystals, and air-dry them at room temperature to obtain the β-form complex. Yield: 1g, yield: 100%. Its crystallographic parameters are as follows:

[0037] Crystallographic parameters of β-type structure complex: C 17 H 12 N2O4Ag,Mr=416.16,triclinic,space groupPī, α=109.97(3)°, β=100.71(3)°, γ=111.30(3)°, Z=2,D c =1.753 g·cm -3 ,μ=1.302mm -1 ,13501 reflectionsmeasured,3587 unique reflections(R int =0.0219), 3424 observed reflections (I>2σ(I), 217 parameters, R1 = 0.0209, wR2 = 0.0550, S = 1.122.

[0038] Figure 4 This is a one-dimensional chain crystal structure diagram of the β-type structure;

[0039] Figure 5 This is a two-dimensional supramolecular crystal structure diagram of the β-type structure;

[0040] Figure 6 The topological structure diagram of the two-dimensional supramolecule with β-type structure;

[0041] Figure 7 This is the three-dimensional supramolecular structure diagram of the β-type structure;

[0042] Figure 8 This is the three-dimensional supramolecular topological structure diagram of the β-type structure.

[0043] 3. Conversion of β-type structural complexes to α-type structural complexes

[0044] Grind 1g of a single crystal of the β-form complex into a powder and place it in a small beaker. Add 50mL of methanol to dissolve the β-form complex completely. Place the beaker in a fume hood and allow the solvent to evaporate at room temperature. After two days, colorless, blocky crystals will be obtained. Filter, collect the crystals, and air-dry at room temperature to obtain the α-form complex. Yield: 1g, yield: 100%.

[0045] 4. Conductivity of α-type and β-type complexes

[0046] The conductivity of the α-type complex was tested to be 30.5±1.4S·cm -1 , where the distance of Ag···Ag is The conductivity of the β-structured complex is 48.2±1.5S·cm -1 , where the distance of Ag···Ag is Compared to the α-type structure, the β-type structure exhibits a 58% increase in conductivity. Due to the induction effect of different solvents, the distance between the central silver metals changes significantly, which leads to a significant change in the material's conductivity. After 10 cycles of continuous conversion between the α-type and β-type structures, their conductivity shows no significant attenuation.

Claims

1. A solvent-induced complex material, characterized in that: The complex material is [(1,2-di(3-pyridyl)ethylene)(1,2,4,5-benzenetetracarboxylate)0.5silver] n , n is the number of repeating units, which is any positive integer; wherein the structural formulas of the 1,2-di(3-pyridyl)ethylene unit and the 1,2,4,5-benzenetetracarboxylate unit are as follows: The complex material has a homogeneous polycrystalline structure, which is α-type and β-type respectively; The crystal of the α-type structure belongs to the triclinic crystal system, the space group is Pī, and the unit cell parameters are α=81.46(3)°, β=85.75(3)°, γ=72.75(3)°; The β-type crystal belongs to the triclinic system, the space group is Pī, and the unit cell parameters are α=109.97(3)°, β=100.71(3)°, γ=111.30(3)°.

2. A method for preparing the complex material according to claim 1, characterized in that The steps include: Dissolve 1,2-di(3-pyridyl)ethylene, 1,2,4,5-benzenetetracarboxylic acid, and silver nitrate in a reactor, add methanol solvent, slowly stir to dissolve the reactants, and slowly evaporate the solvent at room temperature. After 3 days, colorless block crystals can be collected, which is the α-type structure complex; The collected blocky α-type crystals are ground and dissolved in acetonitrile solvent, and the solution is slowly evaporated at room temperature, filtered and washed to collect colorless long strip crystals, which are single crystals of the β-type complex.

3. The preparation method according to claim 2, wherein: The molar ratio of the 1,2-di(3-pyridyl)ethylene, 1,2,4,5-benzenetetracarboxylic acid and silver nitrate is 1-2:1-2:1-2.

4. An application of the complex material according to claim 1, characterized in that: The conversion of different crystal forms of the complex material can be achieved through different solvents, thereby achieving the regulation of the material conductivity; In acetonitrile solvent, the α-type complex is converted into a β-type structure, and the conductivity of the complex material is significantly improved; in methanol solvent, the β-type complex is converted into an α-type structure, and the conductivity of the complex material is significantly decreased.

Images