Externally Regulated Specific Molecular Recognition Driven Pathway Selectivity in Supramolecular Polymerization |
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Authors: | Anwesha Chakraborty Dr. Rabindra Nath Manna Prof. Dr. Ankan Paul Prof. Dr. Suhrit Ghosh |
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Affiliation: | 1. School of Applied and Interdisciplinary Sciences Indian Association for the Cultivation of Science, Kolkata, 2A and 2B Raja S. C. Mullick Road, India-, 700032;2. School of Chemical Sciences Indian Association for the Cultivation of Science, Kolkata, 2A and 2B Raja S. C. Mullick Road, India-, 700032 |
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Abstract: | This article reveals 4-dimethylaminopyridine (DMAP) regulated pathway selectivity in the supramolecular polymerization of a naphthalene-diimide derivative (NDI-1), appended with a carboxylic acid group. In decane, NDI-1 produces ill-defined aggregate (Agg-1) due to different H-bonding motifs of the −COOH group. With one mole equivalent DMAP, the NDI-1/DMAP complex introduces new nucleation condition and exhibits a cooperative supramolecular polymerization producing J-aggregated fibrillar nanostructure (Agg-2). With 10 % DMAP and fast cooling (10 K/min), similar nucleation and open chain H-bonding with the free monomer in an anti-parallel arrangement produces identical J-aggregate (Agg-2a). With 2.5 % DMAP and slow cooling (1 K/min), a distinct nucleation and supramolecular polymerization pathway emerge leading to the thermodynamically controlled Agg-3 with face-to-face stacking and 2D-morphology. Slow cooling with 5–10 % DMAP produces a mixture of Agg-2a and Agg-3. Computational modelling studies provide valuable insights into the internal order and the pathway complexity. |
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Keywords: | Externally regulated nucleation-elongation Hydrogen-bonding Pathway complexity Kinetic and thermodynamic control Supramolecular polymerization |
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