Photoinduced Electron Transfer within Donor-Spacer-Acceptor Molecular Assemblies Studied by Time-Resolved Microwave Conductivity

2007 ◽  
pp. 571-601 ◽  
Author(s):  
John M. Warman ◽  
Matthijs P. De Haas ◽  
Jan W. Yerhoeven ◽  
Michael N. Paddon-Row
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Molecular Assemblies ◽  
Microwave Conductivity ◽  
Time Resolved

scholarly journals Electron self-exchange activation parameters of diethyl sulfide and tetrahydrothiophene

2013 ◽  
Vol 9 ◽  
pp. 1448-1454
Author(s):  
Martin Goez ◽  
Martin Vogtherr
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Nuclear Polarization ◽  
Activation Barrier ◽  
Activation Parameters ◽  
Radical Cations ◽  
Free Energies ◽  
Time Resolved ◽  
Diethyl Sulfide ◽  
Chemically Induced

Electron transfer between the title compounds and their radical cations, which were generated by photoinduced electron transfer from the sulfides to excited 2,4,6-triphenylpyrylium cations, was investigated by time-resolved measurements of chemically induced dynamic nuclear polarization (CIDNP) in acetonitrile. The strongly negative activation entropies provide evidence for an associative–dissociative electron exchange involving dimeric radical cations. Despite this mechanistic complication, the free energies of activation were found to be well reproduced by the Marcus theory of electron transfer, with the activation barrier still dominated by solvent reorganization.

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