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具有铁磁/反铁磁相互作用的镧系(镨、钕、钆)与2-羟基烟酸配位聚合物的模板合成

Template synthesis of lanthanide (Pr, Nd, Gd) coordination polymers with 2-hydroxynicotinic acid exhibiting ferro-/antiferromagnetic interaction.

作者信息

Xu Na, Shi Wei, Liao Dai-Zheng, Yan Shi-Ping, Cheng Peng

机构信息

Department of Chemistry, Nankai University, Tianjin 300071, PR China.

出版信息

Inorg Chem. 2008 Oct 6;47(19):8748-56. doi: 10.1021/ic800623v. Epub 2008 Aug 23.

Abstract

Lanthanide coordination polymers were synthesized from Pr(III), Nd(III), and Gd(III) salts; 2-hydroxynicotinic acid (Hnica); and MnSO 4.H 2O under hydrothermal conditions. In the absence of (CH 3) 3CCOONa, 1D polymers with an infinite Ln(III)-O-Ln(III) chain structure, [Pr(Hnica)(H 2O) 2SO 4] n ( 1), [Nd(Hnica)(H 2O) 2SO 4] n ( 2), and [Gd(Hnica)(H 2O) 2SO 4] n ( 3), were generated. When (CH 3) 3CCOONa was added to the synthetic systems, 2D coordination polymers {[Pr 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 4), {[Nd 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 5), and {[Gd(Hnica) 2(H 2O) 2]ClO 4.H 2O} n ( 6) were obtained. Complexes 4 and 5 both exhibit Kagome lattice structure, while 6 displays a rhombic grid structure. All complexes were characterized by elemental analysis, IR spectra, UV-vis spectra, and X-ray single-crystal diffraction. The variable-temperature magnetic susceptibility studies reveal ferromagnetic interactions between gadolinium(III) ions in 3 and 6 and antiferromagnetic interactions in 1, 2, 4, and 5.

摘要

镧系配位聚合物是在水热条件下由Pr(III)、Nd(III)和Gd(III)盐、2-羟基烟酸(Hnica)以及MnSO₄·H₂O合成的。在没有(CH₃)₃CCOONa的情况下,生成了具有无限Ln(III)-O-Ln(III)链结构的一维聚合物,即[Pr(Hnica)(H₂O)₂SO₄]ₙ (1)、[Nd(Hnica)(H₂O)₂SO₄]ₙ (2)和[Gd(Hnica)(H₂O)₂SO₄]ₙ (3)。当将(CH₃)₃CCOONa添加到合成体系中时,得到了二维配位聚合物{[Pr₃(Hnica)₆(H₂O)₉].3H₂O.SO₄.NO₃}ₙ (4)、{[Nd₃(Hnica)₆(H₂O)₉].3H₂O.SO₄.NO₃}ₙ (5)和{[Gd(Hnica)₂(H₂O)₂]ClO₄.H₂O}ₙ (6)。配合物4和5均呈现出 Kagome晶格结构,而6呈现出菱形网格结构。所有配合物均通过元素分析、红外光谱、紫外可见光谱和X射线单晶衍射进行了表征。变温磁化率研究表明,3和6中钆(III)离子之间存在铁磁相互作用,而1、2、4和5中存在反铁磁相互作用。

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