Tuning the dimensionality of semiconducting nanostructures by self-assembled tetraphenylethylene substituted corroles

Controlling the dimensionality of nanostructures made from self-assembled macrocyclic systems is tedious because they attain thermodynamic stability through the extended π-conjugated structure. Mainly, corrole-based macrocycles are challenging as they form structures that make it difficult to grow hierarchical assemblies. Herein, three tetraphenylethylene (TPE) appended corroles (1-TPE-Cor, 2-TPE-Cor and 3-TPE-Cor) were developed by substituting one, two or three TPEs at the <i>meso</i> phenyl positions of corroles. Detailed investigations revealed that each TPE substituent influences the molecule's planarity, resulting in significant variations in optical, self-assembly, and electronic properties in the three derivatives. One-dimensional (1D) nanotubes were observed through π-π stacking for 1-TPE-Cor, while 2D nanosheets and nanospheres were seen for 2-TPE-Cor and 3-TPE-Cor. Consequently, the electrical conductivity of 1D nanotubes is 10 times higher than for the 2D and 0D nanostructures. Each TPE substituent on corroles affects their aggregation dynamics and electronic properties, and this study promotes novel corrole-based macrocyclic groups, apart from porphyrin and phthalocyanine, utilizing supramolecular interactions, paving the way to diversification in the field of electronics.