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Title:SULFUR HYDROGEN BONDING: A COMPARISON OF THE DIMERS AND MONOHYDRATES OF THENYL AND FURFURYL ALCOHOLS AND MERCAPTANS
Author(s):Juanes, Marcos
Contributor(s):Jaraiz, Martin; Enriquez, Lourdes; Rubio, José Emiliano; Pinacho, Ruth; Lesarri, Alberto; Saragi, Rizalina Tama
Subject(s):Rotational structure/frequencies
Abstract:\begin{wrapfigure}{r}{0pt} \includegraphics[scale=0.18]{dimer_comb_2_v2.eps} \end{wrapfigure} The dimers of thenyl alcohol (TA$_{2}$) and furfuryl alcohol (FA$_{2}$), and the monohydrates of both alcohols (TA$\cdot$$\cdot$$\cdot$H$_{2}$O, FA$\cdot$$\cdot$$\cdot$H$_{2}$O) and their corresponding mercaptans (TM$\cdot$$\cdot$$\cdot$H$_{2}$O, FM$\cdot$$\cdot$$\cdot$H$_{2}$O) were generated in a supersonic jet expansion and probed using both chirped-pulse and cavity Fourier transform microwave spectroscopy. The experimental results, supported by ab initio molecular orbital calculations, allow comparing the conformational preferences and the role of the sulfur and oxygen atoms in the O-H$\cdot$$\cdot$$\cdot$O/O-H$\cdot$$\cdot$$\cdot$S/S-H$\cdot$$\cdot$$\cdot$O hydrogen bonds (HBs) stabilizing the dimers. In the furfuryl monohydrates (FA$\cdot$$\cdot$$\cdot$H$_{2}$O, FM$\cdot$$\cdot$$\cdot$H$_{2}$O) water behaves as a proton donor to the ring oxygen, in competence with a second HB to the alcohol or thiol side chain\footnote{M.~Juanes, A.~Lesarri, R.~Pinacho, E.~Charro, J.~E.~Rubio, L.~Enriquez, M.~Jaraiz, \textit{Chem.~Eur.~J.}, \textbf{2018}, 24, 1–9, in press}. Different behavior was observed when the ring oxygen is replaced by sulfur atom in the thenyl monohydrates (TA$\cdot$$\cdot$$\cdot$ H$_{2}$O and TM$\cdot$$\cdot$$\cdot$H$_{2}$O) as the water molecule is binding to the side chain and the $\pi$ electronic cloud of the ring. The water motion in both thenyl dimers is detected by tunneling splittings of the rotational transitions, denoting a weaker binding compared to the furfuryl compounds. The alcohol dimers (TA)$_{2}$ and (FA)$_{2}$ again reveal the different HB strengths in the furfuryl and thenyl groups. The alcohol dimer forms a network of two consecutive O-H$\cdot$$\cdot$$\cdot$O hydrogen bonds involving the oxygen ring, while in the thenyl dimer the alcohol group prefers binding to the $\pi$ cloud than to the sulfur atom in the ring. Spectroscopic, structural and computational data will be reported.
Issue Date:06/19/18
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:APS
Genre:Conference Paper / Presentation
Type:Text
Language:English
URI:http://hdl.handle.net/2142/100709
DOI:10.15278/isms.2018.TJ09
Other Identifier(s):TJ09
Date Available in IDEALS:2018-08-17
2018-12-12


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