Understanding the fundamental molecular interactions underpinning self-assembly is a crucial component for the design of self-assembled supramolecular architectures over varied length scales having defined function and composition. Recent experimental observations using STM on the self-assembly of tricarbazole triazolophane macrocycles (tricarb) show the existence of both ordered honeycomb and non-ordered structures at the solution/HOPG surface. Here, we have performed a comparative analysis of three different structural motifs for the self-association and growth of tricarb oligomers using dispersion-corrected density functional theory on appropriate cluster models based on the experimental findings. Our analysis shows a positive cooperativity of the H-bonding contributions to the interaction energies from favorable local dipole orientations from triazole units of the self-assembled molecules. Effective parameters obtained from our theoretical calculations are used to explain the experimentally observed structures, and provide detailed insights into the effect of intermolecular dipole-dipole interactions on the self-assembly process.<br/>

Understanding cooperative interactions in the polymorphs of self-assembled macrocycles

2019 Spring National Meeting

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