Development of functional molecular assemblies based on programmable construction of face-to-face assemblies of metallo-porphyrinoids
Development of functional molecular assemblies based on programmable construction of face-to-face assemblies of metallo-porphyrinoids
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DOI：
10.1007/s10847-019-00969-9
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发表时间：
2020-01
影响因子：
2.3
通讯作者：
Y. Yamada;Kentaro Tanaka
中科院分区：
文献类型：
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作者：
Y. Yamada;Kentaro Tanaka
金属卟啉类化合物具有多种独特的物理和化学性质，这取决于它们的卟啉类骨架结构以及它们的中心金属离子的性质。利用金属卟啉类化合物作为分子模块，制备新型功能分子组装体的一个有用策略是以共面方式组装它们。这样的组件允许协同的部件间电子通信，或部件之间的功能协同性，以实现独特的功能。从这个意义上说，由不同类型的金属卟啉类化合物组成的离散共面组装体的可编程构造是有吸引力的，因为它们的功能可以通过改变各种参数来控制，即组装组件的相对距离、相对角度、数量和性质。然而，由于卟啉类化合物的高度平面结构，它们易于以面对面的几何形状自组装以产生一维聚合物结构，因此以预先设计的方式构建金属卟啉类化合物的不同面对面组装体是具有挑战性的。为了克服这些困难，适当的合成方法是必要的。这些方法大致分为两种方法;一种是利用共价键形成，另一种是利用非共价相互作用。本文综述了可编程构建由各种金属卟啉类化合物组成的离散共面组装体的合成方法。
Metallo-porphyrinoids are known to possess various unique physical and chemical properties depending on their porphyrinoid skeleton structure, as well as the nature of their central metal ions. A useful strategy for the production of novel functional molecular assemblies, utilizing metallo-porphyrinoids as molecular modules, is to assemble them in a cofacial fashion. Such assemblies allow synergistic inter-component electronic communication, or functional cooperativity among the components to achieve unique functions. In this sense, programmable construction of discrete cofacial assemblies composed of different types of metallo-porphyrinoids is appealing because the their functions can be controlled by changing various parameters, namely the relative distance, relative angle, number, and nature of assembled components. However, as porphyrinoids are prone to self-assemble with face-to-face geometry to produce one-dimensional polymeric structures because of their highly planar structure, it is challenging to construct diverse face-to-face assemblies of metallo-porphyrinoids in a pre-designed fashion. In order to overcome these difficulties, appropriate synthetic methodologies are necessary. These are broadly divided into two approaches; one is to utilize covalent bond formation, and the other is to utilize non-covalent interactions. This review summarizes synthetic methodologies applied toward the programmable construction of discrete cofacial assemblies composed of various metallo-porphyrinoids.