Journal
CHEMISTRY-AN ASIAN JOURNAL
Volume 17, Issue 24, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.202201010
Keywords
Charge transfer; cooperative effects; hydrogen bonds; self-assembly; stacking interactions
Categories
Funding
- Netherlands Organization for Scientific Research (NWO)
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Hydrogen-bonded supramolecular systems can obtain extra stabilization through complexation with ions. The presence of ions weakens the hydrogen bonds but strengthens the cooperativity by pulling the monomers closer together. This results in larger steric repulsion but enhanced donor-acceptor interactions, leading to more charge donation and enhanced electrostatic attraction.
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.
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