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The Critical Role Played by the Catalytic Moiety in the Early‐Time Photodynamics of Hydrogen‐Generating Bimetallic Photocatalysts
Author(s) -
Pan Qing,
Mecozzi Francesco,
Korterik Jeroen P.,
Vos Johannes G.,
Browne Wesley R.,
Huijser Annemarie
Publication year - 2016
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.201600458
Subject(s) - bimetallic strip , moiety , photochemistry , excited state , catalysis , ultrafast laser spectroscopy , chemistry , photocatalysis , ligand (biochemistry) , population , metal , spectroscopy , stereochemistry , atomic physics , organic chemistry , biochemistry , physics , receptor , demography , quantum mechanics , sociology
The effect of the catalytic moiety on the early‐time photodynamics of Ru/M (M=Pt or Pd) bimetallic photocatalysts is studied by ultrafast transient absorption spectroscopy. In comparison to the Ru/Pd photocatalyst described earlier, the Ru/Pt analogue shows complex excited‐state dynamics with three distinct kinetic components ranging from sub‐ps to 10 2 ps, requiring a more sophisticated photophysical model than that developed earlier for the Ru/Pd complex. In the Pu/Pt photocatalyst, an additional lower‐lying excited state is proposed to quench the hot higher‐lying triplet metal‐to‐ligand charge‐transfer states. Furthermore, a strong excitation wavelength dependence on the population of excited states is observed for both the Ru/Pt and Ru/Pd complexes, indicating a non‐equilibrated distribution even on the 10 2 ps timescale. These insights shed light on the significant impact of the catalytic moiety on the fundamental early‐time photophysics of Ru‐based photocatalysts.