Template-directed self-assembly of porphyrin nanorings through an imine condensation reaction

Abstract

Template-directed self-assembly has proven to be an extremely effective method for the precise fabrication of biomacromolecules in natural systems, while artificial template-directed self-assembly systems for the preparation of highly intricate molecules remain a great challenge. In this article, we report the template-directed self-assembly of porphyrin nanorings with different cavity sizes from a tetraaldehyde-derived Zn(II) porphyrin and a diamine precursor through an imine condensation reaction. Up to 9 or 18 precursor molecules self-assemble together to produce a triporphyrin nanoring and a hexaporphyrin nanoring in one step, with the assistance of a tripyridine or hexapyridine template, respectively. The imine-linked porphyrin nanorings are further modified by reduction and acylation reactions to obtain more stable nanorings. The open cavities of porphyrin rings enable them to act as effective hosts to encapsulate fullerenes (C₆₀ and C₇₀). This work presents a highly efficient template-directed self-assembly strategy for the construction of complicated molecules by using dynamic covalent chemistry of imine bond formation.