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Sülzner, Niklas ; Geissler, Bastian ; Grandjean, Alexander ; Jung, Gregor ; Nuernberger, Patrick

Excited‐State Proton Transfer Dynamics of a Super‐Photoacid in Acetone‐Water Mixtures

Sülzner, Niklas, Geissler, Bastian, Grandjean, Alexander , Jung, Gregor und Nuernberger, Patrick (2022) Excited‐State Proton Transfer Dynamics of a Super‐Photoacid in Acetone‐Water Mixtures. ChemPhotoChem 6 (7), e202200041.

Veröffentlichungsdatum dieses Volltextes: 26 Jul 2022 09:30
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.52650


Zusammenfassung

Super-photoacids, that is, photoacids with a negative pK(a) value in the electronically excited state, can trigger an excited-state proton transfer (ESPT) to the solvent. For the neutral pyranine-derived super-photoacid studied here, even indications for ESPT in acetoneous solution are reported. The characteristics of ESPT in this environment, that is, which intermediates exist and what the ...

Super-photoacids, that is, photoacids with a negative pK(a) value in the electronically excited state, can trigger an excited-state proton transfer (ESPT) to the solvent. For the neutral pyranine-derived super-photoacid studied here, even indications for ESPT in acetoneous solution are reported. The characteristics of ESPT in this environment, that is, which intermediates exist and what the impact of cosolvents is, remain unsettled though. In this work, we study ESPT in acetone-water mixtures by steady-state and time-resolved fluorescence spectroscopy. Various effects are observed: First, the addition of water supports the formation of a hydrogen-bonded ground-state complex comprising one water molecule and the photoacid, whose excitation triggers the formation of a hydrogen-bonded ion pair on a sub-ns time scale. Second, water has an overall accelerating effect on the fluorescence dynamics of the involved emitting species, whose contributions are disentangled in a global analysis scheme, enabling the identification of emission from the free photoacid, a photoacid-water complex, a hydrogen-bonded ion pair, and the deprotonated photoacid. At least two water molecules are necessary for ESPT in the environment. Third, additional acidification thwarts an efficient ground-state complex formation of the photoacid and water. However, upon excitation, complexation may occur on a timescale faster than the photoacid's excited-state lifetime, so that emission from a nascent complex emerges.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftChemPhotoChem
Verlag:Wiley
Ort der Veröffentlichung:WEINHEIM
Band:6
Nummer des Zeitschriftenheftes oder des Kapitels:7
Seitenbereich:e202200041
Datum14 April 2022
InstitutionenChemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Lehrstuhl für Physikalische Chemie I > Prof. Dr. Patrick Nürnberger
Identifikationsnummer
WertTyp
10.1002/cptc.202200041DOI
Stichwörter / KeywordsGEMINATE RECOMBINATION; STEADY-STATE; PHENOL OH; ION-PAIR; SOLVENT; SOLVATOCHROMISM; SPECTROSCOPY; FLUORESCENCE; ALCOHOLS; CARBON; Eigen-Weller model; excited-state proton transfer; photoacid; solvent effects; time-resolved spectroscopy
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-526502
Dokumenten-ID52650

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