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Hydrogen‐Generating Ru/Pt Bimetallic Photocatalysts Based on Phenyl‐Phenanthroline Peripheral Ligands
Author(s) -
O'Reilly Laura,
Pan Qing,
Das Nivedita,
Wenderich Kasper,
Korterik Jeroen P.,
Vos Johannes G.,
Pryce Mary T.,
Huijser Annemarie
Publication year - 2018
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.201800658
Subject(s) - bimetallic strip , photoexcitation , intersystem crossing , photochemistry , phenanthroline , chemistry , ultrafast laser spectroscopy , ligand (biochemistry) , photoluminescence , bridging ligand , catalysis , spectroscopy , excited state , crystallography , materials science , singlet state , organic chemistry , optoelectronics , biochemistry , physics , receptor , quantum mechanics , nuclear physics , crystal structure
Recent studies on hydrogen‐generating supramolecular bimetallic photocatalysts indicate a more important role of the peripheral ligands than expected, motivating us to design a Ru/Pt complex with 4,7‐diphenyl‐1,10‐phenanthroline peripheral ligands. Photoinduced intra‐ and inter‐ligand internal conversion processes have been investigated using transient absorption spectroscopy, spanning the femto‐ to nanosecond timescale. After photoexcitation and ultrafast intersystem crossing, triplet states localised on either the peripheral ligands or on the bridging ligand/catalytic unit are populated in a non‐equilibrated way. Time‐resolved photoluminescence demonstrates that the lifetime for the Ru/Pt dinuclear species (795±8 ns) is significantly less than that of the mononuclear analogue (1375±20 ns). The photocatalytic studies show modest hydrogen turnover numbers, which is possibly caused by the absence of an excited state equilibrium. Finally, we identify challenges that must be overcome to further develop this class of photocatalysts and propose directions for future research.