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Experimental Evidence for Water Mediated Electron Transfer Through Bis-Amino Acid Donor−Bridge−Acceptor Oligomers

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University of Pittsburgh, Department of Chemistry, Pittsburgh, Pennsylvania 15260, and Temple University, Department of Chemistry, Philadelphia, Pennsylvania 19122
†University of Pittsburgh.
‡Temple University.
Cite this: J. Am. Chem. Soc. 2009, 131, 6, 2044–2045
Publication Date (Web):January 27, 2009
Copyright © 2009 American Chemical Society

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This work compares the photoinduced unimolecular electron transfer rate constants for two different solute molecules (D-SSS-A and D-SRR-A) in water and DMSO solvents. The D-SSS-A solute has a cleft between the electron donor and acceptor units, which is able to contain a water molecule but is too small for DMSO. The rate constant for D-SSS-A in water is significantly higher than that for D-SRR-A, which lacks a cleft, and significantly higher for either solute in DMSO. The enhancement of the rate constant is explained by an electron tunneling pathway that involves water molecule(s).

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Synthesis of D-SSS-A, D-SRR-A, and acceptor only (control) molecules; table of kET for D-SSS-A and D-SRR-A in different solvents; and details of the continuum model calculation. This material is available free of charge via the Internet at

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