Ligand Bridging-Angle-Driven Assembly of Molecular Architectures Based on Quadruply Bonded Mo-Mo Dimers
Ligand Bridging-Angle-Driven Assembly of Molecular Architectures Based on Quadruply Bonded Mo-Mo Dimers
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DOI：
10.1021/ja1080794
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发表时间：
2010-12-15
影响因子：
15
通讯作者：
Zhou, Hong-Cai
中科院分区：
文献类型：
--
作者：
Li, Jian-Rong;Yakovenko, Andrey A.;Zhou, Hong-Cai
本文系统地研究了由刚性有机连接体的桥联角控制的Mo-2（O2 C-）（4）基金属有机分子结构的组装。十二个桥接二羧酸配体被设计成具有不同的尺寸，桥接角为0，60，90和120度，同时掺入各种非桥接官能团，并且这些配体被用作接头。这些二羧酸酯连接体与作为节点的四重键合的Mo-Mo簇组装，得到13种分子结构，称为金属有机多边形/多面体，具有线性形状、三角形、八面体和立方八面体/反立方八面体的金属簇节点排列。对配合物的合成进行了优化，并通过单晶X-射线衍射确定了配合物的结构。结果表明，所得到的分子结构的形状和大小可以通过调节连接体的桥接角和大小来分别控制。连接体的官能化可以调节随后的分子组装的溶解度，但对产物的几何形状几乎没有影响。初步的气体吸附，光谱和电化学性能的选定成员进行了研究。本工作试图通过引入四重键合的Mo-Mo单元来丰富含金属超分子化学，这可以拓宽额外电子功能的前景，从而导致新的性质。
A systematic exploration of the assembly of Mo-2(O2C-)(4)-based metal-organic molecular architectures structurally controlled by the bridging angles of rigid organic linkers has been performed. Twelve bridging dicarboxylate ligands were designed to be of different sizes with bridging angles of 0, 60, 90, and 120 degrees while incorporating a variety of nonbridging functional groups, and these ligands were used as linkers. These dicarboxylate linkers assemble with quadruply bonded Mo-Mo clusters acting as nodes to give 13 molecular architectures, termed metal-organic polygons/polyhedra with metal cluster node arrangements of a linear shape, triangle, octahedron, and cuboctahedron/anti-cuboctahedron. The syntheses of these complexes have been optimized and their structures determined by single-crystal X-ray diffraction. The results have shown that the shape and size of the resulting molecular architecture can be controlled by tuning the bridging angle and size of the linker, respectively. Functionalization of the linker can adjust the solubility of the ensuing molecular assembly but has little or no effect on the geometry of the product. Preliminary gas adsorption, spectroscopic, and electrochemical properties of selected members were also studied. The present work is trying to enrich metal-containing supramolecular chemistry through the inclusion of well-characterized quadruply bonded Mo-Mo units into the structures, which can widen the prospect of additional electronic functionality, thereby leading to novel properties.