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- Title
Unraveling the Coulombic Forces in Electronically Decoupled Bichromophoric Systems during Two Successive Electron Transfers.
- Authors
Ivanov, Maxim V.; Wadumethrige, Shriya H.; Wang, Denan; Rathore, Rajendra
- Abstract
Coulombic forces are vital in modulating the electron transfer dynamics in both synthetic and biological polychromophoric assemblies, yet quantitative studies of the impact of such forces are rare, as it is difficult to disentangle electrostatic forces from simple electronic coupling. To address this problem, the impact of Coulombic interactions in the successive removal of two electrons from a model set of spirobifluorenes, where the interchromophoric electronic coupling is nonexistent, is quantitatively assessed. By systematically varying the separation of the bifluorene moieties using model compounds, ion pairing, and solvation, these interactions, with energies up to about 0.4 V, are absent at distances greater than about 9 Å. These findings can be (quantitatively) applied for the design of polychromophoric assemblies, whereby the redox properties of donors and/or acceptors can be tuned by judicious positioning of the charged groups to control the electron-transfer dynamics.
- Subjects
CHROMOPHORES; CHARGE exchange; ELECTROSTATICS; FLUORENE; ELECTRON donor-acceptor complexes
- Publication
Chemistry - A European Journal, 2017, Vol 23, Issue 37, p8834
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201702211