Supramolecular photochirogenesis
Supramolecular photochirogenesis
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超分子光致手性
DOI：
10.1039/c3cs60339c
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发表时间：
2014
影响因子：
46.2
通讯作者：
Inoue Yoshihisa
中科院分区：
文献类型：
--
作者：
Yang Cheng;Inoue Yoshihisa
超分子光致手性是一个快速发展的跨学科科学领域，处于光化学、不对称合成和超分子化学的边界。超分子光手性相对于传统分子光手性的主要优势在于其起源是熵，这是通过在基态下预组织底物并通过手性超分子介质中弱但非瞬时的相互作用来操纵随后的光化学转化来实现的。通过合作的非共价相互作用以及主体在基态和激发态的限制，手性转移通常变得更加有效。因此，所有的基态和激发态事件，包括络合化学计量和亲和力、手性光学性质、光物理行为和光化学反应性，共同在超分子光手性发生中发挥关键作用。这可能看起来会导致复杂化，但实际上扩大了可操纵因素和可用实验/理论工具的范围，用于从热力学和动力学上阐明机制和控制光致手性过程，从中已经开发了一些超分子光化学独特的新概念/方法，例如非敏化催化光手性和波长控制光手性。在这篇综述中，我们将讨论超分子光手性发生的最新进展和未来前景。
Supramolecular photochirogenesis is a rapidly growing interdisciplinary area of science at the boundary of photochemistry, asymmetric synthesis and supramolecular chemistry. The major advantage of supramolecular photochirogenesis over the conventional molecular one is entropic in origin, being achieved by preorganizing substrate(s) in the ground state and manipulating subsequent photochemical transformation by weak but non-transient interactions in chiral supramolecular media. The chirality transfer often becomes more efficient through the cooperative non-covalent interactions and the confinement by host in both ground and excited states. Thus, all of the ground- and excited-state events, including complexation stoichiometry and affinity, chiroptical properties, photophysical behaviour and photochemical reactivity, jointly play pivotal roles in supramolecular photochirogenesis. This may appear to cause complication but in reality expands the range of manipulable factors and available experimental/theoretical tools for elucidating the mechanism and controlling photochirogenic processes both thermodynamically and kinetically, from which some new concepts/methodologies unique to supramolecular photochemistry, such as non-sensitizing catalytic photochirogenesis and wavelength-controlled photochirogenesis, have already been developed. In this review, we will discuss the recent progress and future perspective of supramolecular photochirogenesis.