Understanding the influence of alkali cations and halogen anions on the cooperativity of cyclic hydrogen-bonded rosettes in supramolecular stacks

Andre Nicolai Petelski*, Célia Fonseca Guerra

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Hydrogen-bonded supramolecular systems are known to obtain extra stabilization from the complexation with ions, like guanine quadruplex (GQ). They experience strong hydrogen bonds due to cooperative effects. To gain deeper understanding of the interplay between ions and hydrogen-bonding cooperativity, relativistic dispersion-corrected density functional theory (DFT-D) computations were performed on triple-layer hydrogen-bonded rosettes of ammeline interacting with alkali metal cations and halides. Our results show that when ions are placed between the stacks, the hydrogen bonds are weakened but, at the same time, the cooperativity is strengthened. This phenomenon can be traced back to the shrinkage of the cavity as the ions pull the monomers closer together and therefore the distance between the monomers becomes smaller. On one hand this results in a larger steric repulsion, but on the other hand, the donor-acceptor interactions are enhanced due to the larger overlap between the donating and accepting orbitals leading to more charge donation and therefore an enhanced electrostatic attraction.

Original languageEnglish
Article numbere202201010
Pages (from-to)1-10
Number of pages10
JournalChemistry - An Asian Journal
Volume17
Issue number24
Early online date7 Nov 2022
DOIs
Publication statusPublished - 14 Dec 2022

Bibliographical note

Funding Information:
We thank the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. A. N. Petelski thanks the National Scientific and Technical Research Council (CONICET) of Argentina for a research position.

Publisher Copyright:
© 2022 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.

Funding

We thank the Netherlands Organization for Scientific Research (NWO) for financial support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. A. N. Petelski thanks the National Scientific and Technical Research Council (CONICET) of Argentina for a research position.

FundersFunder number
SURF Cooperative
Consejo Nacional de Investigaciones Científicas y Técnicas
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

    Keywords

    • Charge transfer
    • cooperative effects
    • hydrogen bonds
    • self-assembly
    • stacking interactions

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