Subporphyrinato boron (subporphyrin) was elusive until the syntheses of tribenzosubporphine in 2006 and meso-aryl-substituted subporphyrin in 2007. These novel contracted analogues possess a 14 electron conjugated system embedded in a bowl-shaped structure. They exhibit absorption and fluorescence in the UV/vis region and nonlinear optical properties due to their octupolar structures. The unique coordination geometry around the central boron atom in the structure of subporphyrin enabled investigation of rare boron species, such as borenium cations, boron hydrides, and boron peroxides. Along with the burgeoning development of the chemistry of subporphyrins, analogous triphyrin systems have also emerged. Their rich coordination chemistry as a result of their free-base structures, which are different from the boron-coordinating structure of subporphyrins, has been intensively investigated. On the basis of the unique structures and reactivities of subporphyrins and their related triphyrin analogues, supramolecular architectures and covalently linked multicomponent systems have also been actively pursued. This Review provides an overview of the development of subporphyrin and triphyrin chemistry in the past decade and future prospects in this field, which may inspire molecular design toward applications based on their unique properties.
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