Electron Sharing and Anion-π Recognition in Molecular Triangular Prisms

摘要

Electronic interactions, as well as through-space electron hopping and delocalization between redox-active aromatic building blocks, play a crucial role in orchestrating electron transport in organic materials. Extensive investigations of orbital overlap associated with both parallel and T-shaped geometries between aromatic rings are paving the way for the design of efficient organic photovoltaics and molecular electronic devices. In any quest to advance these research areas, it is essential to learn how through-space orbital overlap and electron sharing in non-traditional (that is, not parallel or T-shaped) geometries between multiple rings affect the properties of aromatic compounds and their superstructures. With the objective of investigating this phenomenon in molecules with unconventional aromatic stacking geometries, we have designed and synthesized rigid chiral triangular prisms, namely (-)- and (+)-NDI-A, with tubular cavities flanked by three naphthalenediimide (NDI) units. Its unique redox properties and accessible function-alization make NDI an ideal building block with which to explore electron-transport and delocalization. Furthermore, the highly electron-deficient nature of NDIs is of current interest for the investigation of anion-π interactions with potential applications in chemosensing, synthetic membrane transport, and selective catalysis.