Spectroscopic and photophysical studies of apparent cluster-to-organic-acceptor charge transfer in a molecular cadmium sulfide assembly

Dong I. Yoon; Donald C. Selmarten; Hong Lu; Hui Jean Liu; Carolyn Mottley; Mark A. Ratner; Joseph T. Hupp

doi:10.1016/0009-2614(96)00046-2

Spectroscopic and photophysical studies of apparent cluster-to-organic-acceptor charge transfer in a molecular cadmium sulfide assembly

Dong I. Yoon^*, Donald C. Selmarten, Hong Lu, Hui Jean Liu, Carolyn Mottley, Mark A. Ratner, Joseph T. Hupp

^*Corresponding author for this work

Chemistry

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

7 Scopus citations

Abstract

A nitrobenzene (NB) decorated cadmium sulfide cluster, [Cd₄(S-NB)₁₀][N(CH₃)₄]₂, has been prepared and examined spectroscopically. The assembly exhibits an intense cluster-to-attached-acceptor charge-transfer band at 376 nm. Observation of back electron transfer (nitrobenzene to cluster) via time resolved luminescence yields a rate constant of ≥ 5 × 10⁹ s^-1. Raman studies show that seven vibrational modes are coupled to the electron transfer reaction and that those exhibiting the greatest initial-state/final-state displacements are the Cd-S and N-O stretches. Despite the activity of V_Cd-S, however, the electron donor is more appropriately characterized as an individual sulfur atom, rather than a delocalized assembly.

Original language	English (US)
Pages (from-to)	84-89
Number of pages	6
Journal	Chemical Physics Letters
Volume	251
Issue number	1-2
DOIs	https://doi.org/10.1016/0009-2614(96)00046-2
State	Published - Mar 15 1996

Funding

We thank Professor Ken Spears for the generous loan of instrumentation for single photon counting measurements and Professor Steve Boxer for advice on construction of the Stark instrument. We gratefully acknowledge the Office of Naval Research, the DOD AASERT program and the donors to the Petroleum Research Fund, administered by the American Chemical Society, for support of this work. JTH additionally acknowledges a Teacher-Scholar Award (1991-96) from the Dreyfus Foundation.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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@article{3a2e93d6e5ff48fcbb6a9566eab887d4,

title = "Spectroscopic and photophysical studies of apparent cluster-to-organic-acceptor charge transfer in a molecular cadmium sulfide assembly",

abstract = "A nitrobenzene (NB) decorated cadmium sulfide cluster, [Cd4(S-NB)10][N(CH3)4]2, has been prepared and examined spectroscopically. The assembly exhibits an intense cluster-to-attached-acceptor charge-transfer band at 376 nm. Observation of back electron transfer (nitrobenzene to cluster) via time resolved luminescence yields a rate constant of ≥ 5 × 109 s-1. Raman studies show that seven vibrational modes are coupled to the electron transfer reaction and that those exhibiting the greatest initial-state/final-state displacements are the Cd-S and N-O stretches. Despite the activity of VCd-S, however, the electron donor is more appropriately characterized as an individual sulfur atom, rather than a delocalized assembly.",

author = "Yoon, {Dong I.} and Selmarten, {Donald C.} and Hong Lu and Liu, {Hui Jean} and Carolyn Mottley and Ratner, {Mark A.} and Hupp, {Joseph T.}",

note = "Funding Information: We thank Professor Ken Spears for the generous loan of instrumentation for single photon counting measurements and Professor Steve Boxer for advice on construction of the Stark instrument. We gratefully acknowledge the Office of Naval Research, the DOD AASERT program and the donors to the Petroleum Research Fund, administered by the American Chemical Society, for support of this work. JTH additionally acknowledges a Teacher-Scholar Award (1991-96) from the Dreyfus Foundation.",

year = "1996",

month = mar,

day = "15",

doi = "10.1016/0009-2614(96)00046-2",

language = "English (US)",

volume = "251",

pages = "84--89",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier B.V.",

number = "1-2",

}

TY - JOUR

T1 - Spectroscopic and photophysical studies of apparent cluster-to-organic-acceptor charge transfer in a molecular cadmium sulfide assembly

AU - Yoon, Dong I.

AU - Selmarten, Donald C.

AU - Lu, Hong

AU - Liu, Hui Jean

AU - Mottley, Carolyn

AU - Ratner, Mark A.

AU - Hupp, Joseph T.

N1 - Funding Information: We thank Professor Ken Spears for the generous loan of instrumentation for single photon counting measurements and Professor Steve Boxer for advice on construction of the Stark instrument. We gratefully acknowledge the Office of Naval Research, the DOD AASERT program and the donors to the Petroleum Research Fund, administered by the American Chemical Society, for support of this work. JTH additionally acknowledges a Teacher-Scholar Award (1991-96) from the Dreyfus Foundation.

PY - 1996/3/15

Y1 - 1996/3/15

N2 - A nitrobenzene (NB) decorated cadmium sulfide cluster, [Cd4(S-NB)10][N(CH3)4]2, has been prepared and examined spectroscopically. The assembly exhibits an intense cluster-to-attached-acceptor charge-transfer band at 376 nm. Observation of back electron transfer (nitrobenzene to cluster) via time resolved luminescence yields a rate constant of ≥ 5 × 109 s-1. Raman studies show that seven vibrational modes are coupled to the electron transfer reaction and that those exhibiting the greatest initial-state/final-state displacements are the Cd-S and N-O stretches. Despite the activity of VCd-S, however, the electron donor is more appropriately characterized as an individual sulfur atom, rather than a delocalized assembly.

AB - A nitrobenzene (NB) decorated cadmium sulfide cluster, [Cd4(S-NB)10][N(CH3)4]2, has been prepared and examined spectroscopically. The assembly exhibits an intense cluster-to-attached-acceptor charge-transfer band at 376 nm. Observation of back electron transfer (nitrobenzene to cluster) via time resolved luminescence yields a rate constant of ≥ 5 × 109 s-1. Raman studies show that seven vibrational modes are coupled to the electron transfer reaction and that those exhibiting the greatest initial-state/final-state displacements are the Cd-S and N-O stretches. Despite the activity of VCd-S, however, the electron donor is more appropriately characterized as an individual sulfur atom, rather than a delocalized assembly.

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VL - 251

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EP - 89

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-2

ER -

Spectroscopic and photophysical studies of apparent cluster-to-organic-acceptor charge transfer in a molecular cadmium sulfide assembly

Abstract

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