One-dimensional copper-nitroxide free radical coordination polymer as well as preparation method and application thereof

A technology of nitroxide radicals and coordination polymers, applied in copper organic compounds, static memory, instruments, etc., to achieve high application value, high yield and high purity

Inactive Publication Date: 2013-04-03
TIANJIN NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in the synthesis system of nitroxide radical coordination polymers, the more carboxylic acid bridging ligands used are mainly rigid polycarboxylic acids containing benzene rings, such as phthalic acid, terephthalic acid, isophthalic acid, etc. Diacids, pyromellitic acid, etc., and flexible polycarboxylic acid bridging ligands are rarely involved in the synthesis of free radical multidimensional complexes, and there are relatively few reports on such molecular magnetic materials.

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  • One-dimensional copper-nitroxide free radical coordination polymer as well as preparation method and application thereof
  • One-dimensional copper-nitroxide free radical coordination polymer as well as preparation method and application thereof
  • One-dimensional copper-nitroxide free radical coordination polymer as well as preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Complex {[Cu(NIT3Py) 2 (phda)] 2} n ( 1 )Synthesis:

[0040] At room temperature, copper nitrate (0.1 mmol) and meta-pyridine radical ligand (0.2 mmol) were dissolved in a mixed solvent of 10 ml of water and methanol under stirring, stirred for 0.5 hours, and then 5 ml of phthalate was added dropwise Disodium acetate (0.1 mmol) aqueous solution was stirred for 0.5 hours, and filtered to obtain a dark blue solution. The filtrate was left to stand at room temperature and slowly evaporated. After two weeks, green strip-shaped crystals suitable for X-ray analysis were obtained. The yield was 73%.

[0041] Elemental analysis (%) C 68 h 80 Cu 2 N 12 o 16 : Calculated for C 56.38, H 5.57, N 11.61; found for C 56.30, H 5.49, N 11.72. Important infrared spectral values ​​(KBr pellets, cm -1 ): 1612s, 1396m, 1372s.

Embodiment 2

[0043] Complex {[Cu(NIT4Py)(phda)(H 2 O)] 2} n ( 2 )Synthesis:

[0044] At room temperature, copper nitrate (0.1 mmol) and p-pyridine radical ligand (0.2 mmol) were dissolved in a mixed solvent of 10 ml of water and methanol under stirring, stirred for 0.5 hours, and then 5 ml of phthalate was added dropwise Disodium acetate (0.1 mmol) aqueous solution was stirred for 0.5 hours and filtered to obtain a dark blue solution. The filtrate was left to stand at room temperature and slowly evaporated. After about ten days, dark green strip crystals suitable for X-ray analysis were obtained. The yield was 68%.

[0045] Elemental analysis (%)C 44 h 52 Cu 2 N 6 o 14 : Calcd. C 52.01, H 5.16, N 8.27; found C 52.10, H 5.25, N 8.21. Important infrared spectral values ​​(KBr pellets, cm -1 ): 1613s, 1396m, 1372s.

Embodiment 3

[0047] the crystal 1 with 2 Structural analysis: the selected size is 0.11 x 0.11 x 0.08 mm 3 green crystals 1 and 0.15 x 0.14 x 0.13 mm 3 dark green crystals of 2 Fixed on fiberglass. Mo-K monochromated with graphite on a Bruker APEX-II CCD X-ray diffractometer at room temperature α Rays( lambda = 0.71073 ?), with φ - ω A total of 8375 and 10637 diffraction points were collected by scanning methods. The crystal structure was solved by the direct method using the program SHELXS-97 and corrected by full matrix least squares using the program SHELXL-97. The positions of hydrogen atoms were obtained by theoretical hydrogenation, and non-hydrogen atoms were solved by direct methods. The experimental conditions, data analysis, structure analysis and correction methods and crystallographic data of the X-ray diffraction analysis of the complex are listed in Table 1;

[0048] Table 1 Complexes 1 with 2 The crystallographic data of

[0049]

[0050] Results and d...

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Abstract

The invention provides two novel one-dimensional free radical-metal polymers {[Cu(NIT3Py)2(phda)]}n(1) and {[Cu(NIT4Py) (phda)(H2O)]}n(2) prepared by a constant temperature solvent evaporation method by using cupric ions and pyridine free radicals as self-rotating carriers and phenylenediacetic acid as a bridging ligand. The yield and purity of crystals obtained are high. The structure is analyzed by using infrared spectroscopy and X-ray single crystal diffraction and the like. The crystal structure shows that when different pyridine free radicals are used as end group ligands, phenylenediacetic acid is bridged with cupric ions to obtain different one-dimensional chain structures. The magnetic research result shows that pyridine free radicals can control and regulate the magnetic action of the complexes, so that the complexes have a higher potential application value in molecular information storage materials like ferric oxide.

Description

[0001] Statement Regarding Funding Research or Development [0002] This application is supported by the Science and Technology Development Fund of Tianjin Higher Education Institutions (20080503). technical field [0003] The invention belongs to the technical field of molecular magnetic materials, in particular to the preparation method and application of two metal-free radical complexes. Background technique [0004] In the present invention, two one-dimensional chain polymers with different crystal structures are obtained because phthalic acid has different bridging modes, and different pyridine free radicals have the function of regulating molecular magnetism. The research on molecular-based functional materials has become a hot topic in material science research, and the research on the design and synthesis of molecular-based magnetic materials has become one of the most active and challenging topics in the field of molecular materials. Due to the incomparable advanta...

Claims

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Application Information

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IPC IPC(8): C07F1/08H01F1/42G11C11/16
Inventor 高东昭
Owner TIANJIN NORMAL UNIVERSITY
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