Lanthanide complexes with cucurbit[n]urils (n = 5, 6, 7) and perrhenate ligands: new examples of encapsulation of perrhenate anions.
Lanthanide complexes with cucurbit[n]urils (n = 5, 6, 7) and perrhenate ligands: new examples of encapsulation of perrhenate anions.
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DOI：
10.1021/ic900328z
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发表时间：
2009-04
影响因子：
4.6
通讯作者：
P. Thuéry
中科院分区：
文献类型：
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作者：
P. Thuéry
硝酸镧系与葫芦[n]urils （CBn, n = 5,6,7）在过环酸存在的水热条件下反应，其中一些与KNO(3)等其他反应物反应，生成了14个新的配合物，这些配合物在晶体学上进行了表征，并呈现出一些原始的特征。与CB5的五个配合物中，有四个是由镧系离子（Ce, Sm, Gd）和钾封闭的胶囊，并有一个被封装的桥接硝酸盐离子，但第五个是一个一维聚合物，CB5的两个双齿门户与镱络合。所有八种CB6配合物（Ce, Pr, Sm, Gd, Yb, Lu）和CB7的单镱配合物（CB7的第一个镧系配合物被表征）都涉及过氧化物包封，其形式要么桥接在每个三叉戟门户上的镧系离子，要么桥接在CB双齿且阳离子远离门户时的末端，甚至在一种情况下不配位。阳离子在空腔中的取向取决于其配位方式，以及空腔中最短接触的性质。描述了一些原始的结构，特别是在CB6的铈配合物和一种新的钐-CB6夹层配合物中的弯曲链，带状组装。ReO(4)（-）在CB6和CB7中的普遍包封，为研究这些大环的阴离子络合作用开辟了新的视角。
The reaction of lanthanide nitrates with cucurbit[n]urils (CBn, n = 5, 6, 7) under hydrothermal conditions in the presence of perrhenic acid and, for some of them, other reactants such as KNO(3) yielded 14 new complexes which were crystallographically characterized and present some original features. Four of the five complexes with CB5 are capsules closed by a lanthanide ion (Ce, Sm, Gd) on one side and potassium on the other and have an encapsulated bridging nitrate ion, but the fifth is a monodimensional polymer with both bidentate portals of CB5 complexed to ytterbium. All eight CB6 complexes (Ce, Pr, Sm, Gd, Yb, Lu) and the single ytterbium complex of CB7 (the first lanthanide complex of CB7 to be characterized) involve perrhenate encapsulation, in a form which is either bridging the lanthanide ions coordinated at each tridentate portal, or terminal when the CB is bidentate and the cation is further from the portal, or even noncoordinating in one case. The orientation of the cation in the cavity varies depending upon its coordination mode, as well as the nature of the shortest contacts in the cavity. Some original architectures are described, in particular a sinuous chain, ribbonlike assembly in a cerium complex of CB6 and a novel samarium-CB6 sandwich complex. The ubiquitous encapsulation of ReO(4)(-) in CB6 and CB7 may open new perspectives for the investigation of anion complexation by these macrocycles.