CONTROLLING INTRAMOLECULAR H-BOND IN ONIUM IONS BY TUNING LONDON DISPERSION - PAULI REPULSION BALANCE

Chen, Peter

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https://hdl.handle.net/2142/122545 Copy

Description

Title

CONTROLLING INTRAMOLECULAR H-BOND IN ONIUM IONS BY TUNING LONDON DISPERSION - PAULI REPULSION BALANCE

Author(s)

Chen, Peter

Contributor(s)

• Gorbachev, Vladimir
• Tsybizova, Alexandra

Issue Date

2023-06-23

Keyword(s)

Non-covalent interactions

Abstract

London Dispersion is an essential element of structural stability and thus affects chemical reactivity and selectivity. However, estimating London forces is challenging due to the omnipresent solvent or crystal lattice effects that attenuate attractive interactions. Here, we report a spectroscopic study of the intramolecular H-bond in five series of onium ions with a systematic increase in Dispersion energy donors (DEDs). Remarkably, the intramolecular H-bond might be localized/delocalized, and therefore its spectroscopic signature is used as a readout reflecting overall steric effects in the system. Therefore, we can probe a delicate London Dispersion - Pauli Repulsion balance by analyzing 2D PESs, applying different energy decomposition schemes, and performing a comparative analysis of experimental data obtained in the gas phase without any external encumbrances, including messenger tags. [1,2] Finally, considering these findings, we can tune the barrier’s height to achieve the desired reactivity for the intramolecular H-transfer reaction or, in other words, turn the hydrogen bond ON/OFF upon request.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Handle URL

https://hdl.handle.net/2142/122545

DOI

https://doi.org/10.15278/isms.2023.7024

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