Tuning the Binding Strength of even and Uneven Hydrogen-Bonded Arrays with Remote Substituents
| Autor: | Thor van Heesch, Stephanie C. C. van der Lubbe, Célia Fonseca Guerra, Anissa Haim |
|---|---|
| Přispěvatelé: | Theoretical Chemistry, AIMMS |
| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
010304 chemical physics
Hydrogen Hydrogen bond Supramolecular chemistry Substituent chemistry.chemical_element 010402 general chemistry Electrostatics 01 natural sciences Acceptor Article 0104 chemical sciences Delocalized electron Crystallography chemistry.chemical_compound chemistry 0103 physical sciences Atom Physical and Theoretical Chemistry |
| Zdroj: | Van Der Lubbe, S C C, Haim, A, Van Heesch, T & Fonseca Guerra, C 2020, ' Tuning the Binding Strength of even and Uneven Hydrogen-Bonded Arrays with Remote Substituents ', Journal of Physical Chemistry A, vol. 124, no. 45, pp. 9451-9463 . https://doi.org/10.1021/acs.jpca.0c07815 The Journal of Physical Chemistry. a Journal of Physical Chemistry A, 124(45), 9451-9463. American Chemical Society |
| ISSN: | 1089-5639 |
| DOI: | 10.1021/acs.jpca.0c07815 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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