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• W3133639878 endingPage "1859" @default.
• W3133639878 startingPage "1845" @default.
• W3133639878 abstract "Bifunctional or amphoteric photoacids simultaneously present donor (acidic) and acceptor (basic) properties making them useful tools to analyze proton transfer reactions. In protic solvents, the proton exchange between the acid and the base is controlled by the acidity or basicity strength and typically occurs on two different pathways known as protolysis and hydrolysis. We report here how the addition of a formate base will alter the relative importance of the possible reaction pathways of the bifunctional photoacid 7-hydroxyquinoline (7HQ), which has been recently understood to predominantly involve a hydroxide/methoxide transport mechanism between the basic proton-accepting quinoline nitrogen site toward the proton-donating OH group with a time constant of 360 ps in deuterated methanol (CD3OD). We follow the reaction dynamics by probing the IR-active marker modes of the different charged forms of photoexcited 7HQ, and of formic acid (HCOOD) in CD3OD 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." @default.
• W3133639878 created "2021-03-15" @default.
• W3133639878 creator A5031586341 @default.
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• W3133639878 creator A5064856224 @default.
• W3133639878 creator A5079831134 @default.
• W3133639878 date "2021-03-02" @default.
• W3133639878 modified "2023-10-16" @default.
• W3133639878 title "Switching between Proton Vacancy and Excess Proton Transfer Pathways in the Reaction between 7-Hydroxyquinoline and Formate" @default.
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• W3133639878 doi "https://doi.org/10.1021/acs.jpca.0c10191" @default.
• W3133639878 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/7957860" @default.
• W3133639878 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/33651619" @default.
• W3133639878 hasPublicationYear "2021" @default.
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