CN115124730B - Dissimilar metal zirconium-based metal organic framework complex with semiconductor behavior and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of dissimilar metal organic framework materials, and provides a dissimilar metal zirconium-based metal organic framework complex with a semiconductor behavior, a preparation method and an application thereof, wherein the molecular formula of the complex is as follows: [ Zr ] ₆ (μ ₃ ‑OH) ₈ (OH) ₈ ][(Cu ₂ I ₂ )(INA) ₄ ] ₂ Xguest, wherein INA represents isonicotinate. The preparation of the complex of the invention is that ZrCl is weighed in turn ₄ Dissolving CuI and isonicotinic acid in an organic solvent, placing the obtained mixed solution in a reaction kettle, reacting under heating condition, and cooling to obtain the final product. The complex is a rare Kagome type zirconium-based metal organic framework constructed by taking different metal clusters as nodes, has a typical semiconductor behavior, and can be used for preparing semiconductor materials.

Description

A heterometallic zirconium-based metal-organic framework complex with semiconductor behavior and its preparation method and application

technical field

The invention relates to the technical field of heterometallic organic framework materials, in particular to a heterometallic zirconium-based metal organic framework complex with semiconductor behavior and its preparation method and application.

Background technique

Heterometallic organic framework materials have the advantages of two or more metal nodes and organic ligands, and have potential application prospects in many fields, and have attracted the attention of researchers at home and abroad. Due to the coordination competition between metal ions, the synthesis of heterometallic organic frameworks faces great challenges. Zirconium-based heterometallic organic framework materials have the characteristics of low crystallinity and difficulty in obtaining a single crystal structure. Therefore, the design and synthesis of such materials have become particularly difficult.

Contents of the invention

The object of the present invention is to provide a heterometallic zirconium-based metal-organic framework complex with semiconducting behavior, its preparation method and application in view of the above-mentioned problems.

In order to achieve the above object, the technical scheme adopted in the present invention is as follows:

The present invention provides a heterometallic zirconium-based metal-organic framework complex with semiconductor behavior, the chemical formula of which is: [Zr ₆ (μ ₃ -OH) ₈ (OH) ₈ ][(Cu ₂ I ₂ )(INA) ₄ ] ₂ xguest, where INA is isonicotinic acid anion, and guest represents the guest molecule in the channel.

In the present invention, further, the asymmetric unit of the complex contains 0.75 Zr ⁴⁺ ions, 0.5 Cu ⁺ ions, 0.5 I ^– , 1 isonicotinate, 1 OH ^– and 1 μ ₃ -OH; The complex takes tetragonal [Cu ₂ I ₂ ] clusters and dodecahedral [Zr ₆ O ₈ ] clusters as nodes, and forms a novel kagome-type metal-organic framework through the connection of isonicotinate.

c＝13.8480(17)，α＝90.0°，β＝90°，γ＝120°，

In the present invention, further, the complex belongs to the hexagonal crystal system, P6/mmm space group; the unit cell parameters are:

c=13.8480(17), α=90.0°, β=90°, γ=120°,

The present invention also provides a method for preparing the above-mentioned heterometallic zirconium-based metal-organic framework complex, which includes the following steps: successively weigh ZrCl ₄ , CuI and isonicotinic acid and dissolve them in an organic solvent, place the obtained mixed solution in a reaction kettle, and heat Under the conditions of reaction, cooling, that is.

Wherein, the molar ratio of ZrCl ₄ , CuI and isonicotinic acid is 1.5:4:14.6.

Wherein, the organic solvent is N,N-dimethylformamide and acetic acid in a volume ratio of 20:1.

Preferably, the reaction under heating conditions is to raise the temperature to 1115-125° C. at a heating rate of 30° C./h, and then carry out the reaction at this temperature.

In summary, owing to adopting above-mentioned technical scheme, the beneficial effect of the present invention is:

The invention provides a preparation method of a heterometallic zirconium-based organic framework with a novel structure. The complex exhibits semiconducting behavior and can be used to prepare semiconducting materials.

Description of drawings

Fig. 1 is the coordination environment figure of Zr1 in the complex of the present invention;

Fig. 2 is the coordination environment figure of Zr in the complex of the present invention;

Figure 3 is a cluster diagram of [Zr ₆ (μ ₃ -OH) ₈ (OH) ₈ ] ⁸⁺ in the complex of the present invention;

Fig. 4 is the coordination environment figure of Cu1 in the complex of the present invention;

Fig. 5 is a [Cu ₂ I ₂ ] unit diagram in the complex of the present invention;

Fig. 6 is the coordination environment diagram of the ligand in the complex of the present invention;

Figure 7 is a three-dimensional structure diagram of the complex of the present invention;

Figure 8 is a topological diagram of the complex of the present invention;

Fig. 9 is the powder diffraction experiment spectrum and the simulation spectrum of the complex of the present invention;

Fig. 10 is the electrical conductivity diagram of the complex of the present invention at room temperature;

Fig. 11 is a diagram of temperature-varying conductivity of the complex of the present invention.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The present invention provides a heterometallic zirconium-based metal-organic framework complex with semiconductor behavior, the chemical formula of which is: [Zr ₆ (μ ₃ -OH) ₈ (OH) ₈ ][(Cu ₂ I ₂ )(INA) ₄ ] ₂ ·xguest, where INA is isonicotinic acid anion, guest represents the guest solvent molecule in the channel, and both x and guest need a series of characterizations to be determined.

Example 1

Accurately weigh isonicotinic acid (180mg, 1.46mmol), ZrCl ₄ (35mg, 0.15mmo), CuI (76mg, 0.4mmol) into the polytetrafluoroethylene liner of the 25mL reaction kettle, add 8mL N,N- Methylformamide (DMF) and 0.4 mL acetic acid. After mixing evenly, close the inner cover tightly, put it into the stainless steel jacket and tighten it. The reaction kettle was put into an oven, raised to 120° C. at a heating rate of 30° C./h, reacted for 48 hours, and then lowered to room temperature at a cooling rate of 2.5° C./h to obtain orange strip crystals with a yield of about 60% ( based on zirconium salts).

The product obtained in Example 1 is characterized and measured for performance:

1) Structural characterization:

作入射光源，以

扫描方式收集衍射点。配合物的晶体结构通过Shelxtl和Olex2软件由直接法解得，非氢原子坐标和各向异性热参数利用全矩阵最小二乘F²法进行修正。由于孔道中的溶剂分子高度无序，因此采用PLATON软件中的SQUEEZE命令，计算出孔道中的电子数，从而可以粗略推测出晶体结构中的客体分子。相关晶体学参数列于表1中。Under the microscope, select crystals with moderate size, regular shape and clean surface, and use SuperNova type single crystal X-ray diffractometer to adopt Mo Kα rays monochromated by graphite monochromator

as the incident light source, with

Diffraction points are collected by scanning. The crystal structure of the complex was solved by the direct method using Shelxtl and Olex2 software, and the coordinates of non-hydrogen atoms and anisotropic thermal parameters were corrected by the full-matrix least squares F ² method. Since the solvent molecules in the channels are highly disordered, the SQUEEZE command in the PLATON software is used to calculate the number of electrons in the channels, so that the guest molecules in the crystal structure can be roughly estimated. The relevant crystallographic parameters are listed in Table 1.

Table 1

Cu-N键长为

Cu-I键长为

至

它们均处于文献所报道的键长范围内。如图6所示，异烟酸采用μ₃-η¹:η¹:η¹的配位模式，每个异烟酸分子可以与两个Zr(IV)和一个Cu(I)配位。The asymmetric unit of the complex of the present invention contains 0.75 Zr(IV) ions, 0.5 Cu(I) ions, 0.5 I ^– , 1 isonicotinate, 1 OH ^– and 1 μ ₃ -OH . The complex contains two types of Zr(IV) ions: Zr1 coordinates with 8 oxygen atoms, which come from 4 μ ₃ -OH (O1, O1C, O2, O2B) and 4 isonicotinic acid carboxylic acid groups respectively Oxygen atoms (O6, O6B, O6C, O6D) on the group form a double-capped triangular prism configuration (Figure 1); Zr2 also coordinates with 8 oxygen atoms, which come from 4 μ ₃ -OH (O1, O1E , O2, O2D), 2 OH ^– oxygen atoms (O3, O4) and 2 oxygen atoms (O5, O15E) on the isonicotinic acid carboxylic acid group, forming an anti-square prism configuration (Figure 2). Two Zr1 atoms on the axial plane and four Zr2 atoms on the equatorial plane are bridged by 8 μ ₃ -OH to form a dodecahedral [Zr ₆ (μ ₃ -OH) ₈ (OH) ₈ ] ⁸⁺ clusters (Fig. 3). The four-coordinated Cu1 atom coordinates with 2 N atoms (N1, N1F) and 2 I atoms (I1, I2) on the isonicotinic acid radical to form a distorted deformed tetrahedral configuration (Figure 4). Two Cu atoms and two I ^– ions constitute a planar quadrilateral [Cu ₂ I ₂ ] unit (Fig. 5). Zr-O bond length is

The Cu-N bond length is

The Cu-I bond length is

to

They are all within the range of bond lengths reported in the literature. As shown in Figure 6, isonicotinic acid adopts the coordination mode of μ ₃ -η ¹ :η ¹ :η ¹ , and each molecule of isonicotinic acid can be coordinated with two Zr(IV) and one Cu(I).

Each [Zr ₆ (μ ₃ -OH) ₈ (OH) ₈ ] ⁸⁺ cluster is connected to 8 [Cu _{2 I 2 ] clusters via 8 isonicotinic acid ions, and each [Cu 2 I 2} ] cluster is connected to 8 [Cu ₂ I ₂ ] clusters via 4 Isonicotinic acid is connected with four [Zr ₆ (μ ₃ -OH) ₈ (OH) ₈ ] ⁸⁺ clusters, and then forms a kagome-type three-dimensional framework with hexagonal and triangular channels. The inner diameters of these two channels are respectively 2.6nm and 1.3nm (Figure 7). Simplify [Zr ₆ (μ ₃ -OH) ₈ (OH) ₈ ] ⁸⁺ clusters and [Cu ₂ I ₂ ] into nodes and isonicotinic acid into lines, respectively, and then form the csq topology of 8,4 connections, The topological notation is {4 ¹⁶ .6 ¹² }{4 ⁴ .6 ² } ₂ (Figure 8).

c＝13.8480(17)，α＝90.0°，β＝90°，γ＝120°，

The complex belongs to the hexagonal system, P6/mmm space group. The unit cell parameters are:

c=13.8480(17), α=90.0°, β=90°, γ=120°,

2) Semiconductor performance measurement:

In order to characterize the semiconducting properties of the complexes, the electrical tests were carried out on Keithley 4200A-SCS and probe station lakeshore instruments. Grind the sample into a uniform powder with a mortar and put it into a standard circular tableting mold with a diameter of 3mm. Press for 20 minutes under a pressure of 0.5T to obtain a compacted disc sample. Use a vernier caliper to measure the thickness of the wafer, apply the conductive silver paste evenly on the upper and lower surfaces and connect the gold wire. Use the two-electrode method to apply a voltage of -5V to 5V, test the change of current and obtain its IV volt-ampere curve. Combine the formula σ=L/(R S) to calculate the conductivity of the sample, where σ: conductivity; L: the thickness of the circular sample measured by the vernier caliper; R: the resistance obtained by the slope of the volt-ampere characteristic curve; S: The cross-sectional area of the disc sample. From Figure 10, it can be concluded that the conductivity of the samples is 1.95×10 ^-8 S/cm.

In addition, the samples were tested for changes in conductivity under variable temperature conditions. As shown in Figure 11, as the temperature increases, the current increases gradually, the resistance decreases gradually, and the conductivity increases gradually, indicating that the complex has typical semiconductor behavior.

The above description is a detailed description of the preferred feasible embodiments of the present invention, but the embodiments are not used to limit the scope of the patent application of the present invention. All equivalent changes or modifications completed under the technical spirit suggested by the present invention shall belong to The scope of patents covered by the present invention.

Claims (7)

1. A dissimilar metal zirconium based metal organic framework complex having semiconducting behavior characterized by: the chemical formula is as follows: [ Zr ] ₆ (μ ₃ -OH) ₈ (OH) ₈ ][(Cu ₂ I ₂ )(INA) ₄ ] ₂ Xguest, where INA is isonicotinic acid anion and guest represents guest molecules in the pore channel; the asymmetric unit of the complex contains 0.75 Zr ⁴⁺ Ion, 0.5 Cu ⁺ Ion, 0.5I _– 1 isonicotinate radical, 1 OH ^– And 1 μ ₃ -OH; the complex is in quadrilateral [ Cu ] ₂ I ₂ ]Cluster and dodecahedron [ Zr ] ₆ O ₈ ]The clusters are nodes and are connected through isonicotinate to form a kagome type metal organic framework; the complex belongs to a hexagonal system, P6/mmm space group; the unit cell parameters are as follows:

c＝13.8480(17)，α＝90.0°，β＝90°，γ＝120°，/>

2. the method of preparing a dissimilar metal zirconium based metal-organic framework complex according to claim 1, comprising the steps of: weighing ZrCl in sequence ₄ Dissolving CuI and isonicotinic acid in an organic solvent, placing the obtained mixed solution in a reaction kettle, reacting under a heating condition, and cooling to obtain the product.

3. The method for preparing a dissimilar metal zirconium-based metal-organic framework complex according to claim 2, wherein: said ZrCl ₄ The molar ratio of CuI to isonicotinic acid is 1.5:4:14.6.

4. the method for preparing a dissimilar metal zirconium-based metal-organic framework complex according to claim 2, wherein: the volume ratio of the organic solvent is 20:1, and acetic acid.

5. The method for preparing a dissimilar metal zirconium-based metal-organic framework complex according to claim 2, wherein: the reaction is heated to 115-125 ℃ at the heating rate of 30 ℃/h under the heating condition, and then the reaction is carried out at the temperature.

6. Use of the dissimilar metal zirconium-based metal-organic framework complex of claim 1 in the manufacture of a semiconductor material.

7. Use of the isometal zirconium-based metal-organic framework complex prepared by the preparation method of any one of claims 2 to 5 in the preparation of semiconductor materials.

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