Comparison of the Photoinduced Electron Transfer Reaction in a Rigid Cyclophane and Its Corresponding Bimolecular Donor/Acceptor Complex

Autor:	Stuart H. Pullen, Shannon L. Studer-Martinez, Amanda L. Harris, Heinz A. Staab, John D. Simon, Alan Long, Maurice D. Edington, Steven W. Baldwin
Rok vydání:	1999
Předmět:	Photoexcitation Reaction rate chemistry.chemical_compound Electron transfer Chemistry Physical and Theoretical Chemistry Proton-coupled electron transfer Donor acceptor Photochemistry Acceptor Photoinduced electron transfer Cyclophane
Zdroj:	The Journal of Physical Chemistry A. 103:10220-10225
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp991973s
Popis:	The back electron transfer following photoexcitation of the bimolecular charge-transfer complex between 1,4-dimethoxybenzene (DMB) and 7,7-dicyanobenzoquinone methide (DCBM) is compared to the dynamics observed for the corresponding spatially constrained cyclophanes. In a recent letter (J. Phys. Chem. 1999, 103, 2740), we reported that the back electron transfer dynamics for two structurally related cyclophanes of DMB and DCBM were identical and that these data provided direct evidence for the through-bond mechanism of electron transfer in this bridged organic donor/acceptor systems. The study of the noncovalent bimolecular system herein enables us to experimentally determine the through-space electron transfer rate for this charge transfer pair. We find that the rate of back electron transfer is faster in the cyclophane than in the bimolecular complex. This difference in reaction rates can be accounted for quantitatively using the Bixon−Jortner equation for the electron transfer reaction rate, if the dif...
Databáze:	OpenAIRE
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