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首页> 外文期刊>Chemistry: A European journal >Competing supramolecular Interactions Give a new Twist to Terpyridyl chemistry: Anion- and Solvent-Induced Formation of spiral Arrays in Silver(I) complexes of a simple Terpyridine
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Competing supramolecular Interactions Give a new Twist to Terpyridyl chemistry: Anion- and Solvent-Induced Formation of spiral Arrays in Silver(I) complexes of a simple Terpyridine

机译：竞争性的超分子相互作用为三联吡啶化学带来了新的变化：阴离子和溶剂诱导的简单三联吡啶银（I）配合物中螺旋阵列的形成

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摘要

Multiple competing molecular interactions (metal - ligand, #pi#-stacking and hydrogen-bonding) in the silver(I) complexes of 4'-thiomethyl-2,2':6',2''-terpyridine give rise to a range of different molecular architectures, in which the metal-ligand coordination requirements are satisfied in quite different ways. Polynuclear supramolecular spirals, aggregated mononuclear and aggregated dinuclear units are all structurally characterised. The metallo-supramolecular architecture obtained displays a remarkable dependence both on the choice of non-coordinated anion and the type of solvent used (coordinating or non-coordinating). The anion dependence is particularly surprising, since the anions are not integrated into the centre of the supramolecular structure. The solution behaviour is also solvent and anion dependent, with aggregation of planar mononuclear cations observed in acetonitrile, but oligonuclear spiral species implicated in nitromethane. The extraordinarily variable geometries of these systems suggest that they provide a novel example of the "frustration" principle, in which opposing tendencies cannot simultaneously be satisfied and identify an alternative approach to the design of metallo-supramolecular systems whose structure is responsive to external agents.
机译：4'-硫代甲基-2,2'：6'，2''-三联吡啶的银（I）配合物中的多个竞争分子相互作用（金属-配体，＃pi＃-堆积和氢键）产生一个范围不同的分子结构，其中金属-配体配位要求以完全不同的方式得到满足。多核超分子螺旋，聚集的单核和聚集的双核单元均具有结构特征。所获得的金属-超分子结构显示出对非配位阴离子的选择和所用溶剂类型（配位或非配位）的显着依赖性。阴离子依赖性特别令人惊讶，因为阴离子没有整合到超分子结构的中心。溶液的行为还取决于溶剂和阴离子，在乙腈中观察到平面单核阳离子的聚集，但在硝基甲烷中涉及寡核螺旋物质。这些系统的几何形状异常可变，表明它们提供了一个“挫折”原理的新颖示例，在这种原理中，不能同时满足相反的趋势，并确定了一种设计对结构响应外部因素的金属-超分子系统的替代方法。

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