Rapid long range intramolecular electron transfer within a steroid molecule with two electron binding groups

Article abstract of DOI:10.1063/1.445696

Intramolecular electron tarnsfer has been observed to have occurred in less than 100 ns in a steroid molecule having two distinct electron binding groups separated by distances distributed from 7-11 Angstroem.Experiments were carried out in organic glasses at 77 K with pulse radiolysis techniques to create trapped electrons which were captured by a group on one end of the steroid molecule.Although one of the groups, benzoate, is held to the steroid spacer by a flexible linkage, the rigidity of the glassy matrices prevented movement to alter the initial distance.Interestingly, no effects of distance were seen: all ET processes appeared to have occurred much faster than our 100 ns time resolution, consistent with measurements of the rate of intermolecular electron transfer between the same functional groups in random solutions.Solvation energetics, on the other hand, had a remarkable influence on the extent and direction of electron transfer.A change in solvent polarity was observed to reverse the direction of electron transfer.Evidence was obtained for a distribution of solvation environments for ions in glasses which may be as broad as 0.15 eV.

Full text of DOI:10.1063/1.445696

Rapid long range intramolecular electron transfer within a steroid molecule with two
electron binding groupsa)
R. Kurt Huddleston and John R. Miller
Citation: The Journal of Chemical Physics 79, 5337 (1983); doi: 10.1063/1.445696
View online: http://dx.doi.org/10.1063/1.445696
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/79/11?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
On: Mon, 22 Dec 2014 10:37:07

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
On: Mon, 22 Dec 2014 10:37:07

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
On: Mon, 22 Dec 2014 10:37:07

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
On: Mon, 22 Dec 2014 10:37:07

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
On: Mon, 22 Dec 2014 10:37:07

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 138.26.31.3
On: Mon, 22 Dec 2014 10:37:07