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Issue 6, 2021
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Tailoring the cavities of hydrogen-bonded amphidynamic crystals using weak contacts: towards faster molecular machines

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Abstract

This work describes the use of C–H⋯F–C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors 1–3I. The crystal structures of these rotors, determined by synchrotron radiation experiments at different temperatures, show the presence of such C–H⋯F–C contacts between extended carbazole stators featuring fluorinated phenyl rings and the 1,4-diazabicyclo[2.2.2]octane (DABCO) rotator. According to the 2H NMR results, using deuterated samples, and periodic density functional theory computations, the rotators experience fast angular displacements (preferentially 120° jumps) due to their low rotational activation energies (Ea = 0.8–2.0 kcal mol−1). The higher rotational barrier for 1 (2.0 kcal mol−1) is associated with a larger number of weak C–H⋯F–C contacts generated by the stators. This strategy offers the possibility to explore the correlation among weak intermolecular forces, cavity shape, and internal dynamics, which has strong implications in the design of future fine-tuned amphidynamic crystals.

Graphical abstract: Tailoring the cavities of hydrogen-bonded amphidynamic crystals using weak contacts: towards faster molecular machines

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Supplementary files

Article information


Submitted
26 Oct 2020
Accepted
14 Dec 2020
First published
14 Dec 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 2181-2188
Article type
Edge Article

Tailoring the cavities of hydrogen-bonded amphidynamic crystals using weak contacts: towards faster molecular machines

A. Navarro-Huerta, M. J. Jellen, J. Arcudia, S. J. Teat, R. A. Toscano, G. Merino and B. Rodríguez-Molina, Chem. Sci., 2021, 12, 2181
DOI: 10.1039/D0SC05899H

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