Rotation in an Enantiospecific Self-Assembled Array of Molecular Raffle Wheels

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Abstract

Tailored nano-spaces can control enantioselective adsorption and molecular motion. We report on the spontaneous assembly of a dynamic system—a rigid kagome network with each pore occupied by a guest molecule—employing solely 2,6-bis(1H-pyrazol-1-yl)pyridine-4-carboxylic acid on Ag(111). The network cavity snugly hosts the chemically modified guest, bestows enantiomorphic adsorption and allows selective rotational motions. Temperature-dependent scanning tunnelling microscopy studies revealed distinct anchoring orientations of the guest unit switching with a 0.95 eV thermal barrier. H-bonding between the guest and the host transiently stabilises the rotating guest, as the flapper on a raffle wheel. Density functional theory investigations unravel the detailed molecular pirouette of the guest and how the energy landscape is determined by H-bond formation and breakage. The origin of the guest's enantiodirected, dynamic anchoring lies in the specific interplay of the kagome network and the silver surface.

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Meier, D., Adak, A. K., Knecht, P., Reichert, J., Mondal, S., Suryadevara, N., … Papageorgiou, A. C. (2021). Rotation in an Enantiospecific Self-Assembled Array of Molecular Raffle Wheels. Angewandte Chemie - International Edition, 60(52), 26932–26938. https://doi.org/10.1002/anie.202107708

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