A Crystallographic Story of Snakes and Ladders: Encapsulated Water Polymers and Rigid Metal Complexes Based on Mono-N-substituted Carboxylate 4,4′-Bipyridine
A Crystallographic Story of Snakes and Ladders: Encapsulated Water Polymers and Rigid Metal Complexes Based on Mono-N-substituted Carboxylate 4,4′-Bipyridine
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DOI：
10.1021/cg801285u
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发表时间：
2009-03
影响因子：
3.8
通讯作者：
Andrew D. Phillips;Zhaofu Fei;W. Ang;R. Scopelliti;P. Dyson
中科院分区：
文献类型：
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作者：
Andrew D. Phillips;Zhaofu Fei;W. Ang;R. Scopelliti;P. Dyson
合成了一种新的两性离子二齿配体，将 4,4'-联吡啶核心和羧酸盐基团作为单个结构单元，专门设计用于合理构建超分子结构（金属有机框架），该结构能够封装和排列水聚集体，从而形成扩展的聚合物网络。特别是，发现单取代的4,4'-联吡啶的末端N'端和羧酸氧很容易以直接的方式与水中的不同过渡金属卤化物配位，提供具有各种结构基序的杂环配合物。然而，对于所结合的水结构的稳定性和形状至关重要的是，由于金属键合的羧酸盐基团的未结合氧中心施加的方向影响而产生强氢键。对剑桥结构数据库的搜索表明，只有少数配合物具有游离羧酸盐......
A new zwitterionic bidentate ligand was synthesized incorporating a 4,4′-bipyridine core with a carboxylate group as a single building block, specifically designed for the rational construction of supramolecular structures (metal−organic frameworks) that are capable of encapsulating and aligning water aggregates leading to the formation of extended polymeric networks. In particular, both the terminal N′ end and a carboxylate oxygen of the monosubstituted 4,4′-bipyridine was found to readily coordinate in a straightforward manner with different transition metal halides in water, affording heterocyclic complexes featuring various structural motifs. However, critical to the stability and shape of the incorporated water structures is the presence of strong hydrogen bonding resulting from the directional influence exerted by an unbound oxygen center of the metal-bonded carboxylate groups. A search of the Cambridge Structural Database reveals that only a small number of complexes that feature a free carboxylate...