Molecular Balances Based on Aliphatic CH-π and Lone-Pair-π Interactions.
CH···π and lone-pair···π interactions are estimated for a series of conformationally dynamic bicyclic N-aryliimides. On the basis of their strengths and mutual synergy/competition, the molecules prefer a folded/unfolded conformation. Calculations suggest strategies to selectively isolate the folded form by increasing the strength of the attractive CH···π interaction or removing the lone-pair···π repulsion. While the barrier for the folded ⇄ unfolded transformation is too large to conformationally lock the molecules in either of the conformers, the dynamics for hopping of the alkyl group across rings and tumbling over the rings are found to be facile in the folded conformation.
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Kerala-695016, India.
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Nijamudheen
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Kerala-695016, India.
Deepthi
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Jose
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Kerala-695016, India.
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Shine
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Kerala-695016, India.
Ayan
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Datta
conformational flexibility; molecular motors; molecular recognition; weak intermolecular forces