Tuning the Binding Strength of even and Uneven Hydrogen-Bonded Arrays with Remote Substituents

Stephanie C.C. Van Der Lubbe, Anissa Haim, Thor Van Heesch, Célia Fonseca Guerra*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We investigated the tunability of hydrogen bond strength by altering the charge accumulation around the frontier atoms with remote substituents. For pyridine···H2O with NH2 and CN substituted at different positions on pyridine, we find that the electron-withdrawing CN group decreases the negative charge accumulation around the frontier atom N, resulting in weakening of the hydrogen bond, whereas the electron-donating NH2 group increases the charge accumulation around N, resulting in strengthening of the hydrogen bond. By applying these design principles on DDAA-AADD, DADA-ADAD, DAA-ADD, and ADA-DAD hydrogen-bonded dimers, we find that the effect of the substituent is delocalized over the whole molecular system. As a consequence, systems with an equal number of hydrogen bond donor (D) and acceptor (A) atoms are not tunable in a predictable way because of cancellation of counteracting strengthening and weakening effects. Furthermore, we show that the position of the substituent and long-range electrostatics can play an important role as well. Overall, the design principles presented in this work are suitable for monomers with an unequal number of donor and acceptor atoms and can be exploited to tune the binding strength of supramolecular building blocks.

Original languageEnglish
Pages (from-to)9451-9463
Number of pages13
JournalJournal of Physical Chemistry A
Volume124
Issue number45
Early online date15 Oct 2020
DOIs
Publication statusPublished - 12 Nov 2020

Funding

We thank The Netherlands Organization for Scientific Research (NWO/CW) for financial support.

FundersFunder number
NWO/CW
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

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