Molecular Architectonics of Stereochemically Constrained π‐Complementary Functional Modules. Issue 26 (24th July 2013)

• Record Type: Journal Article
• Authors: Avinash, M. B.; Samanta, Pralok K.; Sandeepa, K. V.; Pati, Swapan K.; Govindaraju, T.
• Is Part Of: European journal of organic chemistry. Issue 26(2013)
• Page Start: 5838
• Page End: 5847
• Publication Date: 2013-07-24
• Subjects: Charge transfer -- Molecular ­programming -- Molecular architectonics -- Amino acids -- Self‐assembly; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201300677
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: The 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 molecules1 –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 of1 –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. Abstract : In a quest to master pre‐programmed molecular assemblies, we show that alternate stacking over self‐sorting of functional aromatic modules can be energetically controlled by smarter molecular design. Furthermore, by introducing structural mutations into the side‐chain of amino acid auxiliaries, the molecular assemblies form tailored well‐defined 1D and 2D supramolecular nanoarchitectures.