Switching between Proton Vacancy and Excess Proton Transfer Pathways in the Reaction between 7-Hydroxyquinoline and Formate
Marius-Andrei Codescu, Moritz Weiß, Martin Brehm, Oleg Kornilov, Daniel Sebastiani, Erik T. J. Nibbering
Abstract
OD solution. A comparison of the transient IR spectra as a function of formate concentration, and classical molecular dynamics simulations enables us to identify distinct contributions of "tight" (meaning "contact") and "loose" (i.e., "solvent-separated") 7HQ-formate reaction pairs in our data. Our results suggest that depending on the orientation of the OH group with respect to the quinoline aromatic ring system, the presence of the formate molecule in a proton relay pathway facilitates a net proton transfer from the proton-donating OH group of 7HQ-N* via the methanol/formate bridge toward the quinoline N site.
Topics & Concepts
ChemistryFormateBifunctionalQuinolinePhotochemistryProtonHydroxideFormic acidInorganic chemistryOrganic chemistryCatalysisQuantum mechanicsPhysicsPhotochemistry and Electron Transfer StudiesRadical Photochemical ReactionsPhotochromic and Fluorescence Chemistry