Fan Jian, Zhu Hui-Fang, Okamura Taka-Aki, Sun Wei-Yin, Tang Dagger Wen-Xia, Ueyama Norikazu
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China, Fax: (+86) 25-331-4502.
Chemistry. 2003 Oct 6;9(19):4724-31. doi: 10.1002/chem.200305089.
Complex [Ag(tpba)N(3)] (1) was obtained by reaction of novel tripodal ligand N,N',N"-tris(pyrid-3-ylmethyl)-1,3,5-benzenetricarboxamide (TPBA) with [Ag(NH(3))(2)]N(3). While the reactions between 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (TITMB) and silver(I) salts with different anions and solvent systems give six complexes: Ag(3)(titmb)(2)(3).CH(3)OH.4 H(2)O (2), Ag(3)(titmb)(2)(2)(OH).5 H(2)O (3), [Ag(3)(titmb)(2)][Ag(NO(3))(3)]NO(3).H(2)O (4), Ag(3)(titmb)(2)(py)(3).H(2)O (py=pyridine) (5), Ag(3)(titmb)(2)(py)(3) (6), and Ag(3)(titmb)(2)(3).CHCl(3) (7). The structures of these complexes were determined by X-ray crystallography. The results of structural analysis of complexes 1 and 2, with the same azide anion but different ligands, revealed that 1 is a twofold interpenetrated 3D framework with interlocked cage-like moieties, while 2 is a M(3)L(2) type cage-like complex with a methanol molecule inside the cage. Entirely different structure and topology between 1 and 2 indicates that the nature of organic ligands affected the structures of assemblies greatly. While in the cases of complexes 2-7 with flexible tripodal ligand TITMB, they are all discrete M(3)L(2) type cages. The results indicate that the framework of these complexes is predominated by the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and solvents. It is interesting that there is a divalent anion Ag(NO(3))(3) inside the cage 4 and an anion of ClO(4)(-) or NO(3)(-) spontaneously encapsulated within the cage of complexes 5, 6 and 7.
通过新型三脚架配体N,N',N"-三(吡啶-3-基甲基)-1,3,5-苯三甲酰胺(TPBA)与[Ag(NH₃)₂]N₃反应得到了配合物[Ag(tpba)N₃] (1)。而1,3,5-三(咪唑-1-基甲基)-2,4,6-三甲基苯(TITMB)与具有不同阴离子和溶剂体系的银(I)盐之间的反应得到了六种配合物：Ag₃(titmb)₂₃·CH₃OH·4H₂O (2)、Ag₃(titmb)₂₂(OH)·5H₂O (3)、[Ag₃(titmb)₂][Ag(NO₃)₃]NO₃·H₂O (4)、Ag₃(titmb)₂(py)₃·H₂O (py = 吡啶) (5)、Ag₃(titmb)₂(py)₃ (6)以及Ag₃(titmb)₂₃·CHCl₃ (7)。这些配合物的结构通过X射线晶体学确定。对具有相同叠氮阴离子但配体不同的配合物1和2进行结构分析的结果表明，1是具有互锁笼状部分的二重互穿三维骨架，而2是笼内含有一个甲醇分子的M₃L₂型笼状配合物。1和2之间完全不同的结构和拓扑结构表明有机配体的性质对组装体的结构有很大影响。而在具有柔性三脚架配体TITMB的配合物2 - 7的情况下，它们都是离散的M₃L₂型笼。结果表明这些配合物的骨架主要由有机配体的性质和金属离子的几何需求决定，而受阴离子和溶剂的影响不大。有趣之处在于，在笼4内部存在二价阴离子[Ag(NO₃)₃]²⁻，并且在配合物5、6和7的笼内自发包封有ClO₄⁻或NO₃⁻阴离子。
