基于有机羧酸配体的Co(Ⅲ)/Cu(Ⅱ)配合物的合成、结构及表征

摘要/Abstract

摘要： 在溶剂热条件下,以含卤素有机羧酸3-溴-吡啶-2,6-二甲酸(H₂L)为配体,以硝酸钴、硝酸铜为金属源,合成了两例配合物:[Co(L′)₃](1)和[Cu(L′)₂]_n(2)(HL′=5-溴-吡啶-2-甲酸),通过元素分析(EA)、X射线单晶衍射(SXRD)、X射线粉末衍射(PXRD)、红外光谱(IR)和热重分析(TGA)进行结构表征。X射线单晶衍射结果表明,配体H₂L在反应过程中发生脱羧现象,生成单羧酸配体5-溴-吡啶-2-甲酸。在配合物1中,每个Co(Ⅲ)都位于略微扭曲的八面体几何构型中,不对称单元中含有两个单核单元,单核单元通过C—H…O氢键形成三维超分子结构。配合物2的不对称单元中含有一个Cu(Ⅱ),两个脱质子的L′^-配体,每个Cu(Ⅱ)都是六配位的,位于扭曲的八面体几何构型中。Cu(Ⅱ)由配体连接生成1D链结构,通过C—H…O氢键形成三维超分子结构。此外,研究了两例配合物的热稳定性能。

关键词: 溶剂热合成, 有机羧酸配体, 钴配合物, 铜配合物, 晶体结构, 脱羧

Abstract: Two novel complexes, namely [Co(L′)₃] (1) and [Cu(L′)₂]_n (2) (HL′=5-bromopyridine-2-carboxylic acid), were obtained under solvothermal conditions by the assembly process of organic carboxylate ligand containing halogen (3-bromopyridine-2,6-dicarboxylic acid, H₂L) and Co(NO₃)₂·6H₂O or Cu(NO₃)₂·3H₂O respectively, and characterized by element analysis (EA), X-ray single diffraction (SXRD), X-ray powder diffraction (PXRD), infrared spectroscopy (IR) and thermogravimetric analysis (TGA). The single crystal X-ray diffraction reveals that ligand H₂L transform to HL′ during a decarboxylation process. In the asymmetric unit of 1, there are two mononuclear units. In each unit, central Co(Ⅲ) ion is in a slightly distorted octahedron. Complex 1 shows mononuclear structure, forming a three-dimensional (3D) supramolecular structure via C—H…O hydrogen bonding interactions. The asymmetric unit of 2 contains one central Cu atom and two L′^- ligands. In each unit, central Cu(Ⅱ) ion is in a slightly distorted octahedron. Complex 2 exhibits 1D chain structure, forming a three-dimensional (3D) supramolecular structure via C—H…O hydrogen bonding interactions. Furthermore, the stability property of complexes 1 and 2 was also investigated.

Key words: solvothermal synthesis, organic carboxylic acid ligand, Co complex, Cu complex, crystal structure, decarboxylation

中图分类号:

O641.4

保玉婷, 李海朝, 马琴, 孙赞. 基于有机羧酸配体的Co(Ⅲ)/Cu(Ⅱ)配合物的合成、结构及表征[J]. 人工晶体学报, 2021, 50(11): 2129-2137.

BAO Yuting, LI Haichao, MA Qin, SUN Zan. Synthesis, Structure and Characterization of Co(Ⅲ)/Cu(Ⅱ) Complexes Based on Organic Carboxylic Acid Ligands[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(11): 2129-2137.

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