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; Michael R. Wasielewski

doi:10.1021/jp2016374

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, Michael R. Wasielewski

Weizmann Institute of Science

Research output: Contribution to journal › Article › peer-review

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-2,2′-bipyridineRu(II)Cl₂(CN^tbutyl) ₂, which has favorable energetics, ΔG_CS ≈ -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 (τ_CR = 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.

Original language	English
Pages (from-to)	7533-7540
Number of pages	8
Journal	Journal of Physical Chemistry B
Volume	115
Issue number	23
DOIs	https://doi.org/10.1021/jp2016374
State	Published - 16 Jun 2011

All Science Journal Classification (ASJC) codes

Materials Chemistry
Surfaces, Coatings and Films
Physical and Theoretical Chemistry

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@article{2c6c30bcf69249af871bab7aef717f0b,

title = "Photoinduced singlet charge transfer in a ruthenium(II) perylene-3,4:9,10-bis(dicarboximide) complex",

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-2,2′-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.",

author = "Gunderson, {Victoria L.} and Elisha Krieg and Vagnini, {Michael T.} and Iron, {Mark A.} and Boris Rybtchinski and Wasielewski, {Michael R.}",

note = "Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, DOE [DE-FG02-99ER14999]; U.S.-Israel Binational Science Foundation (BSF) [2006416]This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, DOE, under grant no. DE-FG02-99ER14999 (M.R. W.), and by the U.S.-Israel Binational Science Foundation (BSF), grant no. 2006416. B.R. holds the Abraham and Jennie Fialkow Career Development Chair.",

year = "2011",

month = jun,

day = "16",

doi = "10.1021/jp2016374",

language = "الإنجليزيّة",

volume = "115",

pages = "7533--7540",

journal = "Journal of Physical Chemistry B",

issn = "1520-6106",

publisher = "American Chemical Society",

number = "23",

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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.

N1 - Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, DOE [DE-FG02-99ER14999]; U.S.-Israel Binational Science Foundation (BSF) [2006416]This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, DOE, under grant no. DE-FG02-99ER14999 (M.R. W.), and by the U.S.-Israel Binational Science Foundation (BSF), grant no. 2006416. B.R. holds the Abraham and Jennie Fialkow Career Development Chair.

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 - مقالة

SN - 1520-6106

VL - 115

SP - 7533

EP - 7540

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 23

ER -

Photoinduced singlet charge transfer in a ruthenium(II) perylene-3,4:9,10-bis(dicarboximide) complex

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