Tuning the Dimensionality of Semiconducting Nanostructures by Self-assembled Tetraphenylethylene Substituted Corroles

Abstract

Controlling the dimensionality of nanostructures from the self-assembled macrocyclic systems is tedious because they attain thermodynamically stable through the extended π-conjugated structure. Mainly, corrole-based macrocycles are challenging as they contract 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 at mono, bis and tri TPEs at meso phenyl position of corroles. Detailed investigations revealed that the substituent of each TPE influences the molecule's planarity, resulting in significant variation in optical, self-assembly, and electronic properties in three derivatives. One-dimensional (1D) nanotubes were observed through π-π stacking for 1-TPE-Cor, while 2D nanosheets and nanospheres from 2-TPE-Cor and 3-TPE-Cor. Consequently, electrical conductivity has shown that 1D nanotubes are 10 times higher than 2D and 0D nanostructures. Each TPE substitution on corroles affects their dynamics of aggregates and electronic properties, promoting the novel corrole-based macrocyclic group apart from porphyrin and phthalocyanine utilizing supramolecular interactions pave the way to diversify in fields of electronics.