Synthesis, structure and magnetic properties of cobalt(II) and copper(II) coordination polymers assembled by phthalate and 4-methylimidazole

被引:37
作者
Baca, SG
Malinovskii, ST
Franz, P
Ambrus, C
Stoeckli-Evans, H
Gerbeleu, N
Decurtins, S
机构
[1] Acad Sci R Moldova, Inst Chem, Kishinev, Moldova
[2] Univ Bern, Dept Chem & Biochem, CH-3012 Bern, Switzerland
[3] Univ Neuchatel, Inst Chim, CH-2007 Neuchatel, Switzerland
关键词
phthalate compounds; carboxylate complexes; dicarboxylic acid; cobalt(II); copper(II); coordination polymer; crystal structure; helical chain; magnetic properties;
D O I
10.1016/j.jssc.2004.05.001
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
New coordination polymers [M(Pht)(4-MeIm)(2)(H2O)](n) (M = Co (1), Cu (2); Pht(2-) = dianion of o-phthalic acid; 4-MeIm = 4-methylimidazole) have been synthesized and characterized by IR spectroscopy, X-ray crystallography, thermogravimetric analysis and magnetic measurements. The crystal structures of 1 and 2 are isostructural and consist of [M(4-MeIm)(2)(H2O)] building units linked in infinite 1D helical chains by 1,6-bridging phthalate ions which also act as chelating ligands through two O atoms from one carboxylate group in the case of 1. In complex 1, each Co(II) atom adopts a distorted octahedral N2O4 geometry being coordinated by two N atoms from two 4-MeIm, three O atoms of two phthalate residues and one O atom of a water molecule, whereas the square-pyramidal N2O3 coordination of the Cu(II) atom in 2 includes two N atoms of N-containing ligands, two O atoms of two carboxylate groups from different Pht, and a water molecule. An additional strong O-H...O hydrogen bond between a carboxylate group of the phthalate ligand and a coordinated water molecule join the 1D helical chains to form a 2D network in both compounds. The thermal dependences of the magnetic susceptibilities of the polymeric helical Co(II) chain compound 1 were simulated within the temperature range 20-300 K as a single ion case, whereas for the Cu(II) compound 2, the simulations between 25 and 300 K, were made for a linear chain using the Bonner-Fisher approximation. Modelling the experimental data of compound 1 with MAGPACK resulted in: g = 2.6, \D\ = 62 cm(-1). Calculations using the Bonner-Fisher approximation gave the following result for compound 2: g = 2.18, J = -0.4cm(-1). (C) 2004 Elsevier Inc. All rights reserved.
引用
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页码:2841 / 2849
页数:9
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