Substituent Effects on the Supramolecular Polymerization of 5,15-Dioxaporphyrin

Abstract Peripheral substituents significantly impact supramolecular polymerization, yet the way they collectively influence hierarchical growth in antiaromatic compounds remains to be explored. In this study, we systematically examined how hydrogen-bonding motifs, alkoxy and perfluoroalkoxy side chains, and substitution patterns affect the supramolecular polymerization and assemblies of antiaromatic nickel(II) 5,15-dioxaporphyrin (NiDOP). This work highlights peripheral substituent engineering as a strategy to control them and offers principles for designing functional π-conjugated supramolecular materials.