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Stimuli-responsive chirality inversion of metallohelices and related dynamic metal complexes
Coordination Chemistry Reviews ( IF 20.6 ) Pub Date : 2022-06-07 , DOI: 10.1016/j.ccr.2022.214582
Shigehisa Akine , Hiroyuki Miyake

Metal-coordination structures, which contain coordination bonds with a dynamic nature, are generally useful as a platform for stimuli-responsive molecules and materials. This feature was successfully utilized to obtain various kinds of dynamic chiral metal-containing structures that undergo a chirality inversion. This review illustrates the metal-containing helices and related chiral structures that can undergo stimuli-responsive chirality inversion. They are categorized into several structural types that allow different kinds of chirality inversions, e.g., the Δ/Λ chirality inversion of octahedral complexes and their self-assembled analogues, P/M chirality inversion of helical complexes, inversion of the P/M twist chirality of acyclic, macrocyclic, and cage-like complexes, etc. In principle, the chirality inversion described in this review is not a perfect conversion between enantiomers but diastereomers. The conversion basically involves the reversal of the dynamic chirality based on metal coordination while keeping the invariant carbon-centered chirality in the organic ligands. The chirality inversion is driven by the equilibrium shift caused by external stimuli, e.g., environmental changes such as solvent exchange, dissolution/crystallization, etc., or additives such as a proton, cation, organic molecule, etc., or chemical transformation such as redox reactions. In addition, strategies to control the response speeds and time profiles of the chirality inversion have been developed for some chiral metal-containing systems.



中文翻译:

金属螺旋和相关动态金属配合物的刺激响应手性反转

包含具有动态性质的配位键的金属配位结构通常可用作刺激响应分子和材料的平台。该特征被成功地用于获得各种动态手性含金属结构,这些结构经历了手性反转。本综述说明了可以进行刺激响应手性反转的含金属螺旋和相关手性结构。它们分为几种结构类型,允许不同类型的手性反转,例如八面体配合物及其自组装类似物的 Δ/Λ 手性反转,螺旋配合物的P / M手性反转, P / M的反转无环、大环和笼状配合物等的扭曲手性。原则上,本综述中描述的手性反转不是对映异构体之间的完美转换,而是非对映异构体之间的完美转换。该转化基本上涉及基于金属配位的动态手性的逆转,同时保持有机配体中不变的碳中心手性。手性反转是由外部刺激引起的平衡位移驱动的,例如环境变化如溶剂交换、溶解/结晶等,或添加剂如质子、阳离子、有机分子等,或化学转化如氧化还原反应。此外,已经为一些含手性金属的系统开发了控制手性反转的响应速度和时间分布的策略。

更新日期:2022-06-08
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