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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U2 - 10.1016/0009-2614(94)00996-1
DO - 10.1016/0009-2614(94)00996-1
M3 - Article
AN - SCOPUS:0002545269
VL - 229
SP - 40
EP - 46
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 1-2
ER -