TY - JOUR
T1 - Photoinduced singlet charge transfer in a ruthenium(II) perylene-3,4:9,10-bis(dicarboximide) complex
AU - Gunderson, Victoria L.
AU - Krieg, Elisha
AU - Vagnini, Michael T.
AU - Iron, Mark A.
AU - Rybtchinski, Boris
AU - Wasielewski, Michael R.
PY - 2011/6/16
Y1 - 2011/6/16
N2 - Elucidation of photoinduced charge transfer behavior in organic dye/metal hybrids is important for developing photocatalytic systems for solar energy conversion. We report the synthesis and photophysical characterization of a perylene-3,4:9,10-bis(dicarboximide) (PDI)-ruthenium(II) complex, bis-PDI-2,2′-bipyridineRu(II)Cl2(CNtbutyl) 2, which has favorable energetics, ΔGCS ≈ -1.0 eV, for singlet electron transfer from the Ru complex to PDI. Time-resolved optical spectroscopy reveals that upon selective photoexcitation of PDI, ultrafast charge transfer (<150 fs) from the Ru complex to 1*PDI generates the Ru(III)-PDI-• ion pair. The resulting vibrationally hot Ru(III)-PDI-• ion pair exhibits fast relaxation (τ = 3.9 ps) and charge recombination (τCR = 63 ps). Our experimental and computational (DFT and TDDFT) studies show that energy-preserving photodriven singlet electron transfer can dominate in properly designed organic dye/metal complexes, making them of particular interest for use in artificial photosynthetic systems for solar fuels formation.
AB - Elucidation of photoinduced charge transfer behavior in organic dye/metal hybrids is important for developing photocatalytic systems for solar energy conversion. We report the synthesis and photophysical characterization of a perylene-3,4:9,10-bis(dicarboximide) (PDI)-ruthenium(II) complex, bis-PDI-2,2′-bipyridineRu(II)Cl2(CNtbutyl) 2, which has favorable energetics, ΔGCS ≈ -1.0 eV, for singlet electron transfer from the Ru complex to PDI. Time-resolved optical spectroscopy reveals that upon selective photoexcitation of PDI, ultrafast charge transfer (<150 fs) from the Ru complex to 1*PDI generates the Ru(III)-PDI-• ion pair. The resulting vibrationally hot Ru(III)-PDI-• ion pair exhibits fast relaxation (τ = 3.9 ps) and charge recombination (τCR = 63 ps). Our experimental and computational (DFT and TDDFT) studies show that energy-preserving photodriven singlet electron transfer can dominate in properly designed organic dye/metal complexes, making them of particular interest for use in artificial photosynthetic systems for solar fuels formation.
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U2 - 10.1021/jp2016374
DO - 10.1021/jp2016374
M3 - Article
C2 - 21598951
AN - SCOPUS:79958850175
SN - 1520-6106
VL - 115
SP - 7533
EP - 7540
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 23
ER -