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Title:DISPERSION-DOMINATED ᄍ-STACKED COMPLEXES CONSTRUCTED ON A DYNAMIC SCAFFOLD
Author(s):Nemchick, Deacon
Contributor(s):Vaccaro, Patrick; Cohen, Michael
Subject(s):Clusters/Complexes
Abstract:The non-covalent interactions responsible for $pi$-stacking play crucial roles in many fields of modern chemistry, influencing topics ranging from assembly and recognition in biomolecular systems to the design and function of nano-materials. Owing to the propensity for stronger non-aryl forces (textit{e.g.}, hydrogen bonding) to dominate complex formation, the number of detailed laser-spectroscopic studies on $pi$-bound species is surprisingly limited, with most reported examples focusing on adducts involving combinations of benzene (Bz) and/or substituted-benzene derivatives. A concerted experimental and theoretical effort has been undertaken to explore novel $pi$-stacking motifs based on the non-benzoidal framework of tropolone (TrOH), where the potentially frustrated (tunneling-mediated) transfer of a proton between donor and acceptor sites can afford an textit{in situ} probe of non-covalent binding. Laser-induced fluorescence spectra acquired for the binary TrOH$cdot$Bz complex synthesized under cryogenic free-jet expansion conditions show extensive vibronic features that are red-shifted from the intense textit{~{A}$^{1}$}B$_{2}$$-$textit{~{X}$^{1}$}{A}$_{1}$ absorption resonance of the bare TrOH substrate and display intensity patterns indicative of changing textit{intermolecular} potential-surface topography upon $pi ^{*}leftarrowpi$ electron promotion. These results, as well as spectral signatures from textit{intramolecular} TrOH reaction dynamics, will be discussed, with complimentary quantum-chemical calculations serving to provide new insights into the nature of weak, dispersion-dominated interactions.
Issue Date:24-Jun-15
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:ACS
Genre:CONFERENCE PAPER/PRESENTATION
Type:Text
Language:English
URI:http://hdl.handle.net/2142/79476
Date Available in IDEALS:2016-01-05


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