Understanding structural preferences in ketone-phenol dispersion balances

Zimmermann, C.

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https://hdl.handle.net/2142/107372 Copy

Description

Title

Understanding structural preferences in ketone-phenol dispersion balances

Author(s)

Zimmermann, C.

Contributor(s)

Suhm, Martin A.

Issue Date

2020-06-22

Keyword(s)

Non-covalent interactions

Abstract

\begin{wrapfigure}{r}{0pt} \includegraphics[scale=0.5]{CARBONYL_BALANCE.eps} \end{wrapfigure} Ketone-solvent balances consisting of a hydrogen bond donor docking onto the carbonyl oxygen of an asymmetrically substituted ketone, such as an acetophenone derivative, generate two competing isomers. By experimentally probing the vibrational differences with FTIR spectroscopy in a supersonic jet, the abundance ratio of the two isomers at low temperatures is determined. This allows for the experimental benchmarking of theoretically predicted relative conformational energies on a kJ mol$^{-1}$ or even finer scale.\footnote{H. C. Gottschalk et al., \emph{J. Chem. Phys.}, \textbf{2018}, \emph{148}, 014301.}\footnote{A. Poblotzki et al., \emph{J. Phys. Chem. Lett.}, \textbf{2017}, \emph{8}, 5656.} Previous studies of acetophenone derivatives\footnote{C. Zimmermann et al., \emph{Phys. Chem. Chem. Phys.}, \textbf{2020}, \emph{22}, 2870-2877.} with methanol and \emph{tert}-butyl-alcohol showed good agreement between experiment and theoretical predictions and suggest a systematic cancellation of zero point vibrational energy contributions due to the two comparable docking environments, in contrast to previously presented anisole\footnote{A. Poblotzki et al., \emph{Phys. Chem. Chem. Phys.}, \textbf{2016}, \emph{18}, 27265.}\footnote{M. Heger et al., \emph{Phys. Chem. Chem. Phys.}, \textbf{2015}, \emph{17}, 13045.} and furan\footnote{H. C. Gottschalk et al., \emph{Angew. Chem. Int. Ed.}, \textbf{2015}, \emph{55}, 1921.} complexes. These ketone-solvent balances therefore allow for a more direct benchmark of different electronic structure methods with less need for an accurate vibrational treatment beyond the double harmonic approximation. The influence of London dispersion and steric hindrances on the favored docking site in acetophenone derivative/phenol systems are explored by varying the substituentes of the ketone.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

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http://hdl.handle.net/2142/107372

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Copyright 2020 is held by the Author(s)

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