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Title:Hydrogen Bound Complexes With Tropolone: Binding Motifs, Barrier Heights, And The Search For Bifurcating Systems
Author(s):Nemchick, Deacon
Contributor(s):Vaccaro, Patrick; Chew, Kathryn
Abstract:The potentially frustrated transfer of a proton between the hydroxylic (proton-donating) and ketonic (proton-accepting) oxygen atom centers in tropolone (TrOH) long has served as a model system for the study of coherent (symmetrical) proton-transfer events. A litany of hydrogen-bound complexes [TrOH $\cdot$ X\textit{$_{n}$}] can be formed \textit{in situ} by docking amphoteric ligands onto the TrOH substrate under supersonic free-jet expansion conditions. Binary (\textit{n} = 1) and higher order (\textit{n} = 2, 3, \ldots) complexes formed with formic acid, hydrogen fluoride, acetic acid and propiolic acid (X = FA, HF, AA, and PA) have been synthesized and interrogated using a variety of spectroscopic probes built upon the intense \textit{\~{A}$^{1}$}B$_{2}$$-$\textit{\~{X}$^{1}$}{A}$_{1}$ ($\pi ^{*}\leftarrow\pi$) near-ultraviolet absorption system of bare tropolone, thereby providing vibronically resolved information through combined use of laser-induced fluorescence (LIF), dispersed fluorescence (DF), fluorescence hole-burning (FHB), and stimulated emission pumping (SEP) methods. Experimental results reveal the propensity for binary complexes to adopt a higher-energy external binding motif (ligand attached to the seven membered aromatic ring) over the energetically preferred internal form (ligand bound to the O$-$H$\cdots$O reaction center), where the latter cleft-bound species can undergo unique symmetric (coherent) double proton-transfer reactions. These findings will be discussed in light of supporting quantum-chemical calculations.
Issue Date:2014-06-19
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:Nemchick, D.; Vaccaro, P.; Chew, K. HYDROGEN BOUND COMPLEXES WITH TROPOLONE: BINDING MOTIFS, BARRIER HEIGHTS, AND THE SEARCH FOR BIFURCATING SYSTEMS. Proceedings of the International Symposium on Molecular Spectroscopy, Urbana, IL, June 16-21, 2014. DOI:
Genre:Conference Paper / Presentation
Rights Information:Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License.
Date Available in IDEALS:2014-09-17

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