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Issue 12, 1986
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Proton-transfer spectroscopy. Perturbation of the tautomerization potential

Abstract

The phenomena of excited-state intramolecular proton transfer (phototautomerization) are distinguished in molecular mechanism according to four classes. Intrinsic intramolecular proton transfer (e.g. 3-hydroxyflavone) involves ultra-rapid proton transfer across an internal H-bond. Concerted biprotonic transfer (e.g. 7-azaindole dimers and solvates, benzanilide dimers) involves cooperative double proton transfer in a cyclical complex. Static and dynamic catalysis of proton transfer (e.g. lumichrome, adenine, guanine) involves strong catalysis in doubly H-bonded acetic acid complexes, or a proton transport by H-bonded pyridine. Proton-relay transfer (e.g. 7-hydroxyquinoline, 3-hydroxyxanthone) is suggested as involving multiproton-bridged solvates, which may serve as experimental models for proton relays and proton pumps in biological systems.

Potential functions for proton-transfer spectroscopy are discussed and the perturbations of these potentials by specific solvation and by spectroscopic solvent-cage effects are discussed on the basis of a Born–Oppenheimer spectroscopic solvent-cage model.

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Article type: Paper
DOI: 10.1039/F29868202379
Citation: J. Chem. Soc., Faraday Trans. 2, 1986,82, 2379-2392
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    Proton-transfer spectroscopy. Perturbation of the tautomerization potential

    M. Kasha, J. Chem. Soc., Faraday Trans. 2, 1986, 82, 2379
    DOI: 10.1039/F29868202379

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