基于 Kläui 三齿配体和三氰根合金属的六核 Fe(III)2Co(III)2M(II)2 (M = Cu, Ni, Mn)簇合物的合成、结构和磁性

Hexanuclear Fe(III)2Co(III)2M(II)2 (M = Cu, Ni, Mn) clusters based on Kläui's tripodal ligand and tricyanometalates: syntheses, structures and magnetic properties.

机构信息

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, P R China.

出版信息

Dalton Trans. 2011 Mar 14;40(10):2204-12. doi: 10.1039/c0dt00954g. Epub 2010 Dec 13.

DOI:10.1039/c0dt00954g

PMID:21152625

Abstract

With the use of Kläui's tripodal ligand, (Cp)Co(P(O)(OEt)(2))(3) (L(CoEt), Cp = cyclopentadiene) as the auxiliary ligand to react with different metal salts and tricyanometalate building blocks, five neutral trimetallic hexanuclear complexes: [(Tp)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·6H(2)O (1, Tp = hydridotris(pyrazolyl)borate), [(Tp*)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·2H(2)O (2, Tp* = hydridotris(3,5-dimethyl-pyrazolyl)borate), [(pzTp)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·H(2)O·3MeOH (3, pzTp = tetra(pyrazolyl)borate), [(Tp)(2)Fe(2)(CN)(6)Ni(2)(L(CoEt))(2)(MeCN)(2)]·2MeCN·2H(2)O (4) and [(Tp)(2)Fe(2)(CN)(6)Mn(2)(L(CoEt))(2)(MeCN)(2)]·2MeCN (5), have been obtained and structurally characterized. Magnetic measurements confirm that there are ferromagnetic couplings between the cyano-bridged Fe and Cu/or Ni ions and antiferromagnetic interaction between the cyano-bridged Fe and Mn ions. Slow relaxation of the magnetization is observed in complexes 1 and 4, while complex 3 exhibits metamagnetic behavior with a critical field of 17.5 kOe.

摘要

使用 Kläui 的三脚架配体，[(Cp)Co(P(O)(OEt)(2))(3)]-（L(CoEt)，Cp=环戊二烯）作为辅助配体与不同的金属盐和三氰基金属构建块反应，得到了五个中性三金属六核配合物：[(Tp)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·6H(2)O（1，Tp=氢代三（吡唑基）硼酸盐），[(Tp*)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·2H(2)O（2，Tp*=氢代三（3,5-二甲基吡唑基）硼酸盐），[(pzTp)(2)Fe(2)(CN)(6)Cu(2)(L(CoEt))(2)]·H(2)O·3MeOH（3，pzTp=四（吡唑基）硼酸盐），[(Tp)(2)Fe(2)(CN)(6)Ni(2)(L(CoEt))(2)(MeCN)(2)]·2MeCN·2H(2)O（4）和[(Tp)(2)Fe(2)(CN)(6)Mn(2)(L(CoEt))(2)(MeCN)(2)]·2MeCN（5），并对它们进行了结构表征。磁性测量证实，氰桥连的 Fe 和 Cu/或 Ni 离子之间存在铁磁耦合，而氰桥连的 Fe 和 Mn 离子之间存在反铁磁相互作用。配合物 1 和 4 中观察到磁化强度的缓慢弛豫，而配合物 3 表现出具有 17.5 kOe 临界场的变磁行为。