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 language | English |
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Article number | e202201010 |
Pages (from-to) | 1-10 |
Number of pages | 10 |
Journal | Chemistry - An Asian Journal |
Volume | 17 |
Issue number | 24 |
Early online date | 7 Nov 2022 |
DOIs | |
Publication status | Published - 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.
Funders | Funder number |
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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