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.

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基于金属卟啉面对面组装的可编程构建的功能分子组装的开发

已知金属卟啉具有各种独特的物理和化学性质，这取决于它们的卟啉骨架结构，以及它们中心金属离子的性质。利用金属卟啉作为分子模块生产新型功能性分子组装体的一种有用策略是以共面方式组装它们。此类组件允许组件间的协同电子通信或组件之间的功能协作以实现独特的功能。从这个意义上说，由不同类型的金属卟啉组成的离散共面组件的可编程构造很有吸引力，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，由于卟啉类化合物具有高度平面结构，易于以面对面的几何形状自组装以产生一维聚合物结构，因此在预先设计的金属卟啉类化合物中构建多种面对面的组装具有挑战性时尚。为了克服这些困难，需要适当的合成方法。这些大致分为两种方法；一种是利用共价键形成，另一种是利用非共价相互作用。本综述总结了应用于由各种金属卟啉组成的离散共面组件的可编程构建的合成方法。以预先设计的方式构建不同的金属卟啉类化合物具有挑战性。为了克服这些困难，需要适当的合成方法。这些大致分为两种方法；一种是利用共价键形成，另一种是利用非共价相互作用。本综述总结了应用于由各种金属卟啉组成的离散共面组件的可编程构建的合成方法。以预先设计的方式构建不同的金属卟啉类化合物具有挑战性。为了克服这些困难，需要适当的合成方法。这些大致分为两种方法；一种是利用共价键形成，另一种是利用非共价相互作用。本综述总结了应用于由各种金属卟啉组成的离散共面组件的可编程构建的合成方法。