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首页> 外文期刊>Chemistry: A European journal >Interplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates
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Interplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates

机译：控制无环和大环螺旋结构动态转化的相互作用的相互作用

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摘要

A rigid, helical macrocycle that contains two copper(I) ions has been synthesized through subcomponent self-assembly. Although it does not obey the "rule of coordinative saturation", this macrocycle could be prepared through subcomponent substitution starting from a tri(copper(I)) helicate, in a reaction in which copper(I) was ejected. The macrocycle was observed to readily participate in a sequence of transformations between helical structures mediated by the electronic effects of substituents, entropic effects, the conformational preferences of organic building blocks, and the coordinative preferences of the metal ion. The thermodynamic parameters governing the interconversion of an "open" helicate and the "closed" macrocycle were determined through van 't Hoff analysis, allowing quantification of the entropic driving force for macrocyclization.
机译：通过子组件自组装合成了包含两个铜（I）离子的刚性螺旋大环。尽管它不遵守“配位饱和规则”，但该大环化合物可以通过从三（铜（I））螺旋开始喷出铜（I）的反应，通过亚组分取代来制备。观察到大环易于参与由取代基的电子效应，熵效应，有机结构单元的构象偏好和金属离子的配位偏好介导的螺旋结构之间的转化序列。通过van't Hoff分析确定了控制“开放”螺旋和“封闭”大环的相互转化的热力学参数，从而可以量化用于大环化的熵驱动力。

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