Manna Subal Chandra, Zangrando Ennio, Bencini Alessandro, Benelli Cristiano, Chaudhuri Nirmalendu Ray
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata-7000 32, Dipartimento di Scienze Chimiche, University of Trieste, 34127 Trieste, Italy.
Inorg Chem. 2006 Oct 30;45(22):9114-22. doi: 10.1021/ic060807d.
Lanthanide-organic coordination polymeric networks of [Ln(III)2(suc)3(H2O)2].0.5H2O [suc = succinate dianion, Ln = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), and Dy (6)] have been synthesized and characterized by single-crystal X-ray diffraction analyses. The structural determination reveals that complexes are isomorphous, all crystallizing in monoclinic system, space group I2/a(.) The complexes possess a 3D architecture with Ln ion in a nine-coordination geometry attained by eight oxygen atoms from succinate and one oxygen atom from an aqua ligand. Low-temperature magnetic study indicates that ferromagnetic interaction is present in case of Gd(III) and Dy(III). Antiferromagnetic interaction is observed for the rest of the complexes. Density functional theory calculations are performed which support the existence of a superexchange ferromagnetic coupling in Gd(III) ions, whereas classical crystal field model has been applied to study the complexes 1, 2, 3, and 6.
已合成出[Ln(III)₂(suc)₃(H₂O)₂]·0.5H₂O(suc = 琥珀酸二价阴离子,Ln = Pr (1)、Nd (2)、Sm (3)、Eu (4)、Gd (5) 和 Dy (6))的镧系元素 - 有机配位聚合物网络,并通过单晶X射线衍射分析对其进行了表征。结构测定表明这些配合物是同构的,均结晶于单斜晶系,空间群为I2/a(.)。这些配合物具有三维结构,其中Ln离子呈九配位几何构型,由琥珀酸的八个氧原子和一个水合配体的一个氧原子配位形成。低温磁性研究表明,Gd(III) 和 Dy(III) 存在铁磁相互作用。其余配合物观察到反铁磁相互作用。进行了密度泛函理论计算,支持Gd(III) 离子中存在超交换铁磁耦合,而经典晶体场模型已用于研究配合物1、2、3和6。