CN103755633A - 8-aminoquinoline zinc perchlorate metal complex, and preparation method and application thereof - Google Patents

Abstract

The invention discloses an 8-aminoquinoline zinc perchlorate metal complex, a preparation method and an application thereof. Zn(ClO ₄ ) ₂ and 8-aminoquinoline were dissolved in methanol solvent, respectively. The above two solutions were mixed, refluxed under stirring, filtered, and the filtrate was extracted in a non-polar solvent, and a single crystal of the complex with the molecular formula C ₁₈ H ₁₆ C ₁₂ N ₄ O ₈ Zn was obtained after two weeks. The complex forms a three-dimensional supramolecular structure through hydrogen bonding and π...π aromatic ring stacking. Fluorescence spectrophotometer tests show that the substance has excellent fluorescence properties and can be used as a luminescent material.

Description

8-aminoquinoline zinc perchlorate metal complex and its preparation method and application

technical field

The invention belongs to the field of organic synthesis, and relates to an 8-aminoquinoline zinc perchlorate metal complex, a single crystal thereof, a preparation method, and an application of the complex as a luminescent material. the

Background technique

Metal-organic complex fluorescent materials have potential application value in the fields of communication, satellite, radar, optical computer, new battery and biomolecular probe, and are an important part of the family of molecular materials. Molecular design, synthesis and property research of such functional complexes have been widely concerned. The luminescent properties of molecular luminescent materials composed of functional molecules largely depend on the coordination status of ligands and metal ions. The chelation effect formed by the aromatic ring and the metal ion will greatly enhance the efficiency of the material to emit fluorescence. For this reason, choosing 8-aminoquinoline as the metal-organic complex formed by the coordination of organic ligands and metal ions is the preferred material in this field. the

Contents of the invention

The first object of the present invention is to provide a kind of 8-aminoquinoline zinc perchlorate metal complex. The complex forms a three-dimensional supramolecular structure through hydrogen bonding and π...π aromatic ring stacking and has excellent fluorescence properties, and can be used as a potential luminescent material. the

The chemical formula of the 8-aminoquinoline zinc perchlorate metal complex involved in the present invention is (L ₁ ) ₂ ·Zn(ClO ₄ ) ₂ , wherein L ₁ is 8-aminoquinoline.

Second object of the present invention is to provide a kind of preparation method of 8-aminoquinoline zinc perchlorate metal complex. the

In order to achieve the above object, the preparation method of the 8-aminoquinoline zinc perchlorate metal complex of the present invention is: the molar ratio of Zn(ClO ₄ ) ₂ and L ₁ is 1:2, Zn(ClO ₄ ) ₂ and _L1 were all dissolved in methanol solvent, and refluxed under stirring; filtered, the filtrate was extracted in a non-polar extraction solvent, and colorless crystals were obtained after two weeks, filtered, and the filter cake was washed with ether to obtain the target complex; the L ₁ is 8-aminoquinoline.

The time for reflux under stirring is 2 to 6 hours. the

The extraction solvent is diethyl ether or carbon tetrachloride. the

α＝74.9950(10)°，β＝77.4690(10)°，γ＝70.8460(10)°。该配合物的不对称单元中含1个Zn²⁺，2个L₁配体和2个ClO₄ ^-。每个Zn²⁺与来自于两个L₁配体的4个N原子和来自于两个ClO₄ ^-的2个O原子配位，形成扭曲的八面体配位几何构型。分子间弱的氢键和π…π芳香环堆积构成三维超分子结构。其中，八面体的Zn-N键长为

Zn-O键长为

In the invention, zinc perchlorate is selected as a building unit, and 8-aminoquinoline capable of forming hydrogen bonds is used as a bidentate ligand for self-assembly to obtain a metal-organic complex single crystal with a three-dimensional supramolecular structure and fluorescence. Their secondary structural units are: the crystal belongs to the triclinic system, the space group is P-1, and the unit cell parameters are:

α=74.9950(10)°, β=77.4690(10)°, γ=70.8460(10)°. The asymmetric unit of the complex contains 1 Zn ²⁺ , 2 L ₁ ligands and 2 ClO ₄ ^- . Each Zn ²⁺ is coordinated with 4 N atoms from two L ₁ ligands and 2 O atoms from two ClO ₄ ^- , forming a distorted octahedral coordination geometry. The weak intermolecular hydrogen bonds and π…π aromatic ring stacking form a three-dimensional supramolecular structure. Among them, the Zn-N bond length of octahedron is

Zn-O bond length is

The values of N-Zn-N bond angles are 81.03(7)°, 98.97(7)° and 180.0°, respectively. The value of O-Zn-O bond angle is 180.00(8)°. The preparation method of the invention is simple, the raw materials are easy to obtain, and the complex has a three-dimensional supramolecular structure. the

The third object of the present invention is to provide a kind of 8-aminoquinoline zinc perchlorate metal complex as a luminescent material. the

Description of drawings

Fig. 1 is the crystal structure figure of 8-aminoquinoline zinc perchlorate metal complex of the present invention;

Fig. 2 is the packing structure figure of 8-aminoquinoline zinc perchlorate metal complex of the present invention;

Fig. 3 is the solid fluorescence spectrogram of the 8-aminoquinoline zinc perchlorate metal complex of the present invention. the

Detailed ways

The chemical formula of the 8-aminoquinoline zinc perchlorate metal complex of the present invention is (L ₁ ) ₂ ·Zn(ClO ₄ ) ₂ , wherein L ₁ is 8-aminoquinoline.

The present invention will be further described below in conjunction with specific implementation examples. the

Example 1: 0.05mmol Zn(ClO ₄ ) ₂ (13.2mg) and 0.10mmol L ₁ (14.4mg) were respectively dissolved in 10ml of methanol solvent, and the two solutions were mixed at room temperature, refluxed for 2 hours under stirring, and filtered , the filtrate was placed in a 50ml beaker, sealed with a film, and a small hole was pierced, and extracted in an ether pool. After two weeks, colorless crystals were obtained, which were filtered and the filter cake was washed with ether to obtain the target complex with a yield of 51% based on Zn(ClO ₄ ) ₂ .

Example 2: 0.05mmol Zn(ClO ₄ ) ₂ (13.2mg) and 0.10mmol L ₁ (14.4mg) were respectively dissolved in 10ml of methanol solvent, and the two solutions were mixed at room temperature, refluxed for 4 hours under stirring, and filtered , the filtrate was placed in a 50ml beaker, sealed with a film, and a small hole was pierced, and extracted in an ether pool. After two weeks, colorless crystals were obtained, which were filtered and the filter cake was washed with ether to obtain the target complex with a yield of 67% based on Zn(ClO ₄ ) ₂ .

Example 3: 0.05mmol Zn(ClO ₄ ) ₂ (13.2mg) and 0.10mmol L ₁ (14.4mg) were respectively dissolved in 10ml of methanol solvent, and the two solutions were mixed at room temperature, refluxed for 4 hours under stirring, and filtered , the filtrate was placed in a 50ml beaker, sealed with a film, and a small hole was pierced, and extracted in a carbon tetrachloride pool. Two weeks later, colorless crystals were obtained, which were filtered, and the filter cake was washed with ether to obtain the target complex with a yield of 35% based on Zn(ClO ₄ ) ₂ .

Example 4: 0.05mmol Zn(ClO ₄ ) ₂ (13.2mg) and 0.10mmol L ₁ (14.4mg) were respectively dissolved in 10ml of methanol solvent, and the two solutions were mixed at room temperature, refluxed for 6 hours under stirring, and filtered , the filtrate was placed in a 50ml beaker, sealed with a film, and a small hole was pierced, and extracted in a carbon tetrachloride pool. Two weeks later, colorless crystals were obtained, which were filtered, and the filter cake was washed with ether to obtain the target complex with a yield of 54% based on Zn(ClO ₄ ) ₂ .

Embodiment 5: luminescent material, concrete method step is as follows:

The excitation wavelength and emission wavelength of the 8-aminoquinoline zinc perchlorate metal complex were scanned respectively by a fluorescence spectrophotometer, and the optimal wavelength was selected and determined. the

Conclusion: The excitation and emission wavelengths of the complex are 340.0nm and 521.8nm, respectively. the

The structural determination of 8-aminoquinoline zinc perchlorate metal complex of the present invention:

为入射辐射，ω-2θ扫描方式收集室温X-射线单晶衍射数据，最小二乘法精修晶胞参数，SHELXL-97直接法解得晶体结构，全矩阵最小平方二乘法对所有非氢原子位置及各向异性热温度因子进行精修。所有的H原子位置由几何加氢方式确定。详细的晶体测定数据见表1，结构见图1和2，荧光光谱见图3。  The crystal structure was determined using a Bruker Smart Apex II CCD single crystal diffractometer, and Mokα rays monochromated with graphite (

For the incident radiation, the ω-2θ scanning method collects X-ray single crystal diffraction data at room temperature, the least squares method refines the unit cell parameters, the SHELXL-97 direct method solves the crystal structure, and the full matrix least squares method calculates all non-hydrogen atom positions and anisotropic thermal temperature factor for refinement. All H atom positions are determined by geometric hydrogenation. The detailed crystal determination data is shown in Table 1, the structure is shown in Figures 1 and 2, and the fluorescence spectrum is shown in Figure 3.

The crystallographic data of table 1 8-aminoquinoline zinc perchlorate metal complex of the present invention

。

.

Claims (6)

1.8-Aminoquinoline zinc perchlorate metal complex has the following structure:

. 2.8-Aminoquinoline zinc perchlorate metal complex single crystal, characterized in that the single crystal structure adopts a SMART CCD area detector diffractometer with a graphite monochromator, and the X-ray source is MoKα

Diffraction points were collected by ω-2θ scanning, unit cell parameters were corrected by least square method, diffraction data were restored by SAINT program, crystal structure was analyzed using SHELXL-97 software package, and single crystal data were obtained by heavy atom method:

. 3. A complex preparation method as claimed in claim 1, characterized in that: the mol ratio of Zn(ClO ₄ ) ₂ and 8-aminoquinoline is 1: 2, Zn(ClO ₄ ) ₂ and 8-Aminoquinoline was respectively dissolved in methanol solvent, the above two solutions were mixed, and refluxed under stirring; filtered, the filtrate was extracted in a non-polar extraction solvent, and colorless crystals were obtained after two weeks, filtered, and the filter cake was washed with ether, get the target compound. 4. The preparation method of the complex according to claim 3, characterized in that: the time of reflux under stirring is 2 to 6 hours. the 5. The preparation method of the complex as claimed in claim 3, characterized in that: the extraction solvent is diethyl ether or carbon tetrachloride. the 6. Application of 8-aminoquinoline zinc perchlorate metal complex in the preparation of luminescent materials. the

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