Ultrafast Two-Electron Transfer in a CdS Quantum Dot-Extended-Viologen Cyclophane Complex

Ryan M. Young; Stephen C. Jensen; Kedy Edme; Yilei Wu; Matthew D. Krzyaniak; Nicolaas A. Vermeulen; Edward J. Dale; J. Fraser Stoddart; Emily A. Weiss; Michael R. Wasielewski; Dick T. Co

doi:10.1021/jacs.5b13386

Ultrafast Two-Electron Transfer in a CdS Quantum Dot-Extended-Viologen Cyclophane Complex

Ryan M. Young^*, Stephen C. Jensen, Kedy Edme, Yilei Wu, Matthew D. Krzyaniak, Nicolaas A. Vermeulen, Edward J. Dale, J. Fraser Stoddart, Emily A. Weiss, Michael R. Wasielewski, Dick T. Co

^*Corresponding author for this work

Chemistry

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Abstract

Time-resolved optical spectroscopies reveal multielectron transfer from the biexcitonic state of a CdS quantum dot to an adsorbed tetracationic compound cyclobis(4,4′-(1,4-phenylene) bipyridin-1-ium-1,4-phenylene-bis(methylene)) (ExBox⁴⁺) to form both the ExBox^3+• and the doubly reduced ExBox^2(+•) states from a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps. At higher excitation powers the second electron transfer takes ∼5 ps, which leads to a mixture of redox states of the acceptor ligand. The doubly reduced ExBox^2(+•) state has a lifetime of ∼10 ns, while CdS^+•:ExBox^3+• recombines with multiple time constants, the longest of which is ∼300 μs. The long-lived charge separation and ability to accumulate multiple charges on ExBox⁴⁺ demonstrate the potential of the CdS:ExBox⁴⁺ complex to serve as a platform for two-electron photocatalysis.

Original language	English (US)
Pages (from-to)	6163-6170
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	138
Issue number	19
DOIs	https://doi.org/10.1021/jacs.5b13386
State	Published - May 18 2016

Funding

Spectroscopic studies (R.M.Y., D.T.C., S.C.J., K.E., E.A.W., and M.R.W.) were supported as part of the ANSER Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award no. DE-SC0001059. N.A.V., E.J.D., and J.F.S. are part of the Joint Center of Excellence in Integrated Nano-Systems at the King Abdulaziz City for Science and Technology and Northwestern University (NU).

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.5b13386

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title = "Ultrafast Two-Electron Transfer in a CdS Quantum Dot-Extended-Viologen Cyclophane Complex",

abstract = "Time-resolved optical spectroscopies reveal multielectron transfer from the biexcitonic state of a CdS quantum dot to an adsorbed tetracationic compound cyclobis(4,4′-(1,4-phenylene) bipyridin-1-ium-1,4-phenylene-bis(methylene)) (ExBox4+) to form both the ExBox3+• and the doubly reduced ExBox2(+•) states from a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps. At higher excitation powers the second electron transfer takes ∼5 ps, which leads to a mixture of redox states of the acceptor ligand. The doubly reduced ExBox2(+•) state has a lifetime of ∼10 ns, while CdS+•:ExBox3+• recombines with multiple time constants, the longest of which is ∼300 μs. The long-lived charge separation and ability to accumulate multiple charges on ExBox4+ demonstrate the potential of the CdS:ExBox4+ complex to serve as a platform for two-electron photocatalysis.",

author = "Young, {Ryan M.} and Jensen, {Stephen C.} and Kedy Edme and Yilei Wu and Krzyaniak, {Matthew D.} and Vermeulen, {Nicolaas A.} and Dale, {Edward J.} and Stoddart, {J. Fraser} and Weiss, {Emily A.} and Wasielewski, {Michael R.} and Co, {Dick T.}",

note = "Funding Information: Spectroscopic studies (R.M.Y., D.T.C., S.C.J., K.E., E.A.W., and M.R.W.) were supported as part of the ANSER Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award no. DE-SC0001059. N.A.V., E.J.D., and J.F.S. are part of the Joint Center of Excellence in Integrated Nano-Systems at the King Abdulaziz City for Science and Technology and Northwestern University (NU). Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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language = "English (US)",

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AU - Young, Ryan M.

AU - Jensen, Stephen C.

AU - Edme, Kedy

AU - Wu, Yilei

AU - Krzyaniak, Matthew D.

AU - Vermeulen, Nicolaas A.

AU - Dale, Edward J.

AU - Stoddart, J. Fraser

AU - Weiss, Emily A.

AU - Wasielewski, Michael R.

AU - Co, Dick T.

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PY - 2016/5/18

Y1 - 2016/5/18

N2 - Time-resolved optical spectroscopies reveal multielectron transfer from the biexcitonic state of a CdS quantum dot to an adsorbed tetracationic compound cyclobis(4,4′-(1,4-phenylene) bipyridin-1-ium-1,4-phenylene-bis(methylene)) (ExBox4+) to form both the ExBox3+• and the doubly reduced ExBox2(+•) states from a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps. At higher excitation powers the second electron transfer takes ∼5 ps, which leads to a mixture of redox states of the acceptor ligand. The doubly reduced ExBox2(+•) state has a lifetime of ∼10 ns, while CdS+•:ExBox3+• recombines with multiple time constants, the longest of which is ∼300 μs. The long-lived charge separation and ability to accumulate multiple charges on ExBox4+ demonstrate the potential of the CdS:ExBox4+ complex to serve as a platform for two-electron photocatalysis.

AB - Time-resolved optical spectroscopies reveal multielectron transfer from the biexcitonic state of a CdS quantum dot to an adsorbed tetracationic compound cyclobis(4,4′-(1,4-phenylene) bipyridin-1-ium-1,4-phenylene-bis(methylene)) (ExBox4+) to form both the ExBox3+• and the doubly reduced ExBox2(+•) states from a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps. At higher excitation powers the second electron transfer takes ∼5 ps, which leads to a mixture of redox states of the acceptor ligand. The doubly reduced ExBox2(+•) state has a lifetime of ∼10 ns, while CdS+•:ExBox3+• recombines with multiple time constants, the longest of which is ∼300 μs. The long-lived charge separation and ability to accumulate multiple charges on ExBox4+ demonstrate the potential of the CdS:ExBox4+ complex to serve as a platform for two-electron photocatalysis.

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Ultrafast Two-Electron Transfer in a CdS Quantum Dot-Extended-Viologen Cyclophane Complex

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