Photoinduced Singlet Charge Transfer in a Ruthenium(II) Perylene-3,4

May 20, 2011 - M. Kyle Brennaman , Michael R. Norris , Melissa K. Gish , Erik M. Grumstrup , Leila Alibabaei , Dennis L. Ashford , Alexander M. Lapide...
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ARTICLE pubs.acs.org/JPCB

Photoinduced Singlet Charge Transfer in a Ruthenium(II) Perylene-3,4:9,10-bis(dicarboximide) Complex Victoria L. Gunderson,† Elisha Krieg,‡ Michael T. Vagnini,† Mark A. Iron,§ Boris Rybtchinski,*,‡ and Michael R. Wasielewski*,† †

Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208-3113, United States ‡ Department of Organic Chemistry, and §Department of Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel

bS Supporting Information ABSTRACT: 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-2,20 -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 ( 6 ns (3%). The first decay lifetime (3.9 ps) is attributed to vibrational relaxation of the hot Ru(III)PDI• ion pair resulting from charge transfer from Ru(II) to *1PDI (