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Site‐Selective Real‐Time Observation of Bimolecular Electron Transfer in a Photocatalytic System Using L‐Edge X‐Ray Absorption Spectroscopy **
Author(s) -
Britz Alexander,
Bokarev Sergey I.,
Assefa Tadesse A.,
Bajnóczi Èva G.,
Németh Zoltán,
Vankó György,
Rockstroh Nils,
Junge Henrik,
Beller Matthias,
Doumy Gilles,
March Anne Marie,
Southworth Stephen H.,
Lochbrunner Stefan,
Kühn Oliver,
Bressler Christian,
Gawelda Wojciech
Publication year - 2021
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000845
Subject(s) - x ray absorption spectroscopy , photocatalysis , electron transfer , chemistry , spectroscopy , picosecond , absorption spectroscopy , photochemistry , xanes , absorption (acoustics) , triethylamine , ultrafast laser spectroscopy , photosensitizer , materials science , catalysis , laser , optics , organic chemistry , physics , quantum mechanics , composite material
Time‐resolved X‐ray absorption spectroscopy has been utilized to monitor the bimolecular electron transfer in a photocatalytic water splitting system. This has been possible by uniting the local probe and element specific character of X‐ray transitions with insights from high‐level ab initio calculations. The specific target has been a heteroleptic [Ir III (ppy) 2 (bpy)] + photosensitizer, in combination with triethylamine as a sacrificial reductant andFe 3( CO ) 12as a water reduction catalyst. The relevant molecular transitions have been characterized via high‐resolution Ir L‐edge X‐ray absorption spectroscopy on the picosecond time scale and restricted active space self‐consistent field calculations. The presented methods and results will enhance our understanding of functionally relevant bimolecular electron transfer reactions and thus will pave the road to rational optimization of photocatalytic performance.