Department of Chemistry, University of Miami, Coral Gables, FL, 33146, USA.
Chem Soc Rev. 2015 Jan 7;44(1):119-35. doi: 10.1039/c4cs00284a. Epub 2014 Oct 15.
Photochemical and photophysical behavior of molecules in supramolecular assemblies are different and more selective than in gas and isotropic solution phases. Knowledge of the inherent electronic and steric properties of the reactant is insufficient to predict the excited state behavior of molecules confined in such assemblies. Weak interactions between the medium and the reactant as well as the free space in a reaction cavity would play a significant role in modulating the excited state properties of molecules when they are included within confined spaces. The concepts of 'Molecular Photochemistry' should be modified while applying them to 'Supramolecular Photochemistry'. In this review we show that the topochemical rules established to understand reactions in crystals could be extended to supramolecular assemblies in general. To make the best use of the medium one needs to understand the features of the medium, the nature of interaction between the medium and the molecule and the rules that govern the behavior of a molecule in that medium. This tutorial provides introduction to these aspects of 'Supramolecular Photochemistry'.
超分子组装体中分子的光化学和光物理行为与气相和各向同性溶液相中的行为不同，且具有更高的选择性。反应物固有的电子和空间性质的知识不足以预测限制在这种组装体中的分子的激发态行为。反应物与介质之间的弱相互作用以及反应腔中的自由空间在将分子包含在受限空间内时，会在调节分子的激发态性质方面发挥重要作用。在将“分子光化学”的概念应用于“超分子光化学”时，应该对其进行修正。在这篇综述中，我们表明，可以将建立来理解晶体中反应的拓扑化学规则扩展到一般的超分子组装体。为了充分利用介质，人们需要了解介质的特点、介质与分子之间的相互作用的性质以及控制分子在该介质中行为的规则。本教程介绍了“超分子光化学”的这些方面。
