Ultrafast photoinduced charge-shift reactions in electron donor-acceptor 9-arylacridinium ions

Guilford Jones; Mohammad S. Farahat; Scott R. Greenfield; David J. Gosztola; Michael R. Wasielewski

doi:10.1016/0009-2614(94)00996-1

Ultrafast photoinduced charge-shift reactions in electron donor-acceptor 9-arylacridinium ions

Guilford Jones^*, Mohammad S. Farahat, Scott R. Greenfield, David J. Gosztola, Michael R. Wasielewski

^*Corresponding author for this work

Chemistry

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

54 Scopus citations

Abstract

Charge-shift species arising from intramolecular electron transfer have been identified for 9-aryl derivatives of the 10-methyl-acridinium ion through observation of red-shifted fluorescence emission bands and the appearance of radical (ion) transients (CH₃CN and CH₂Cl₂ solvents) using laser flash photolysis. Rates of forward and return charge-shift processes have been determined, the former occurring in the 1 ps time domain with small effects associated with changes in solvent and the electron donor substituent. Rates for return electron transfer were a strong function of the donor oxidation potential and showed acceleration with decreased driving force (inverted behavior). The lifetimes for charge-shift intermediates could be 'tuned' over three orders of magnitude as the result of changes in acridinium structure and solvent.

Original language	English (US)
Pages (from-to)	40-46
Number of pages	7
Journal	Chemical Physics Letters
Volume	229
Issue number	1-2
DOIs	https://doi.org/10.1016/0009-2614(94)00996-1
State	Published - Oct 21 1994

Funding

Support of this research by the Department of Energy, Office of Basic Energy Sciences,D ivision of Chemical Sciences,i s gratefully acknowledged.S RG would like to acknowledget he support of the Distin-guishedP ostdoctoralR esearchP rogram sponsoredb y the US DOE Office of Science Education and Technical Information. We also wish to thank Ding-Xue Yan for technical support.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/0009-2614(94)00996-1

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@article{a8dca3d9d2e74cf68e26cfb34031d016,

title = "Ultrafast photoinduced charge-shift reactions in electron donor-acceptor 9-arylacridinium ions",

abstract = "Charge-shift species arising from intramolecular electron transfer have been identified for 9-aryl derivatives of the 10-methyl-acridinium ion through observation of red-shifted fluorescence emission bands and the appearance of radical (ion) transients (CH3CN and CH2Cl2 solvents) using laser flash photolysis. Rates of forward and return charge-shift processes have been determined, the former occurring in the 1 ps time domain with small effects associated with changes in solvent and the electron donor substituent. Rates for return electron transfer were a strong function of the donor oxidation potential and showed acceleration with decreased driving force (inverted behavior). The lifetimes for charge-shift intermediates could be 'tuned' over three orders of magnitude as the result of changes in acridinium structure and solvent.",

author = "Guilford Jones and Farahat, \{Mohammad S.\} and Greenfield, \{Scott R.\} and Gosztola, \{David J.\} and Wasielewski, \{Michael R.\}",

note = "Funding Information: Support of this research by the Department of Energy, Office of Basic Energy Sciences,D ivision of Chemical Sciences,i s gratefully acknowledged.S RG would like to acknowledget he support of the Distin-guishedP ostdoctoralR esearchP rogram sponsoredb y the US DOE Office of Science Education and Technical Information. We also wish to thank Ding-Xue Yan for technical support.",

year = "1994",

month = oct,

day = "21",

doi = "10.1016/0009-2614(94)00996-1",

language = "English (US)",

volume = "229",

pages = "40--46",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier B.V.",

number = "1-2",

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TY - JOUR

T1 - Ultrafast photoinduced charge-shift reactions in electron donor-acceptor 9-arylacridinium ions

AU - Jones, Guilford

AU - Farahat, Mohammad S.

AU - Greenfield, Scott R.

AU - Gosztola, David J.

AU - Wasielewski, Michael R.

N1 - Funding Information: Support of this research by the Department of Energy, Office of Basic Energy Sciences,D ivision of Chemical Sciences,i s gratefully acknowledged.S RG would like to acknowledget he support of the Distin-guishedP ostdoctoralR esearchP rogram sponsoredb y the US DOE Office of Science Education and Technical Information. We also wish to thank Ding-Xue Yan for technical support.

PY - 1994/10/21

Y1 - 1994/10/21

N2 - Charge-shift species arising from intramolecular electron transfer have been identified for 9-aryl derivatives of the 10-methyl-acridinium ion through observation of red-shifted fluorescence emission bands and the appearance of radical (ion) transients (CH3CN and CH2Cl2 solvents) using laser flash photolysis. Rates of forward and return charge-shift processes have been determined, the former occurring in the 1 ps time domain with small effects associated with changes in solvent and the electron donor substituent. Rates for return electron transfer were a strong function of the donor oxidation potential and showed acceleration with decreased driving force (inverted behavior). The lifetimes for charge-shift intermediates could be 'tuned' over three orders of magnitude as the result of changes in acridinium structure and solvent.

AB - Charge-shift species arising from intramolecular electron transfer have been identified for 9-aryl derivatives of the 10-methyl-acridinium ion through observation of red-shifted fluorescence emission bands and the appearance of radical (ion) transients (CH3CN and CH2Cl2 solvents) using laser flash photolysis. Rates of forward and return charge-shift processes have been determined, the former occurring in the 1 ps time domain with small effects associated with changes in solvent and the electron donor substituent. Rates for return electron transfer were a strong function of the donor oxidation potential and showed acceleration with decreased driving force (inverted behavior). The lifetimes for charge-shift intermediates could be 'tuned' over three orders of magnitude as the result of changes in acridinium structure and solvent.

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Ultrafast photoinduced charge-shift reactions in electron donor-acceptor 9-arylacridinium ions

Abstract

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