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Titel: Solvent‐Controlled Intermolecular Proton‐Transfer Follows an Irreversible Eigen‐Weller Model from fs to ns
VerfasserIn: Grandjean, Alexander
Pérez Lustres, J. Luis
Jung, Gregor
Sprache: Englisch
Titel: ChemPhotoChem
Bandnummer: 5
Heft: 12
Seiten: 1094– 1105
Verlag/Plattform: Wiley
Erscheinungsjahr: 2021
Freie Schlagwörter: Eigen-Weller model
excited states
proton transfer
solvent relaxation
transient absorption spectroscopy
DDC-Sachgruppe: 500 Naturwissenschaften
Dokumenttyp: Journalartikel / Zeitschriftenartikel
Abstract: Intermolecular Proton Transfer (PT) dynamics can be best studied by optical spectroscopy, which can cover the vast timescale spanned by the process. PT in a hydrogen bonding complex between a pyranine-based photoacid and a trialkyl-phosphine oxide is addressed. The photoreaction is traced with the help of femtosecond transient absorption and picosecond-resolved fluorescence. Characteristic kinetics and spectra of the intervening species are isolated by global analysis and spectral decomposition of time-resolved fluorescence. It is found that the shared proton shifts towards the phosphine site upon photoexcitation in acetonitrile. The process occurs on the sub-picosecond timescale, essentially, under solvent control. Despite the ultrafast rate, an equilibrium between the complex and the hydrogen-bonded ion pair (HBIP) is established. Further reaction steps are delayed to the nanosecond timescale, where formation of the excited deprotonated form is observed. The far-reaching consistency between the various methods supports an irreversible Eigen-Weller mechanism in the excited state.
DOI der Erstveröffentlichung: 10.1002/cptc.202100177
Link zu diesem Datensatz: urn:nbn:de:bsz:291--ds-354493
hdl:20.500.11880/32372
http://dx.doi.org/10.22028/D291-35449
ISSN: 2367-0932
Datum des Eintrags: 9-Feb-2022
Bezeichnung des in Beziehung stehenden Objekts: Supporting Information
In Beziehung stehendes Objekt: https://chemistry-europe.onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fcptc.202100177&file=cptc202100177-sup-0001-misc_information.pdf
Fakultät: NT - Naturwissenschaftlich- Technische Fakultät
Fachrichtung: NT - Chemie
Professur: NT - Prof. Dr. Gregor Jung
Sammlung:SciDok - Der Wissenschaftsserver der Universität des Saarlandes



Diese Ressource wurde unter folgender Copyright-Bestimmung veröffentlicht: Lizenz von Creative Commons Creative Commons