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2024-01-01

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cc-by (c) Almacellas, David, et al., 2024
Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/218757

Non-Innocent π Linkers Affect Cooperativity in Hydrogen-Bonded Macrocycles

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https://doi.org/10.1002/ceur.202300036

Abstract

Rigid, linear π-conjugated acetylene linkers connecting a hydrogen-bond acceptor to a hydrogen-bond donor are established building blocks for self-assembled hydrogen-bonded macrocycles. Kohn-Sham molecular orbital and Voronoi deformation density analyses reveal that the acetylene linker plays an unprecedented, non-innocent role in the cooperativity of these hydrogen-bonded macrocycles. The acetylene linker can abstract electron density from the hydrogen-bond acceptor and donor, due to the linkers’ low-lying π-LUMO. As a result, the hydrogen-bond acceptor becomes less negatively charged, which both hampers the cooperativity, as well as the hydrogen bond strength, in the hydrogen-bonded macrocycles. This effect becomes more pronounced when the size of the acetylene linker increases. The findings presented in this work can act as design principles for the development of novel supramolecular macrocycles based on hydrogen bonds.

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ADN, Hidrogen, Química supramolecular

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DNA, Hydrogen, Supramolecular chemistry

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Articles publicats en revistes (Química Inorgànica i Orgànica)
Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))

Citation

ALMACELLAS, David, et al. Non-Innocent π Linkers Affect Cooperativity in Hydrogen-Bonded Macrocycles. Chemistry-A European Journal. 2024. Vol. 2, num. e202300036. ISSN 0947-6539. [consulted: 9 of August of 2026]. Available at: https://hdl.handle.net/2445/218757

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