Molecular Architectonics of Stereochemically Constrained π‐Complementary Functional Modules

Abstract

AbstractThe elucidation of the complex factors that govern recognition events at the molecular level represents a daunting challenge in our quest to master the art of pre‐programmed molecular assemblies. In this context, we present the molecular architectonics of thoughtfully designed amino acid appended functional molecules 1–5. Naphthalenediimide (NDI) and pyrene were employed as functional modules due to their unusual topological shape similarity as well as complementary π‐acidic and π‐basic character, respectively. In addition, we show that dyads of such unusual functional modules energetically favour alternate assembly in contrast to the predominant self‐sorted assembly observed for single‐component systems. Moreover, by incorporating minute structural mutations into the amino acid side‐chains of 1–5, we successfully tailored their assemblies into well‐defined supramolecular architectures, namely supercoiled helices, twisted nanoribbons, nanobelts, comb‐edged nanoflakes and nanosheets. A detailed analysis with the aid of experimental and theoretical studies has generated interesting insights into the factors that govern the recognition events at the molecular level.