Unraveling the Coulombic Forces in Electronically Decoupled Bichromophoric Systems during Two Successive Electron Transfers

Authors

Maxim V. Ivanov, Marquette University
Shriya Wadumethrige, Marquette University
Denan Wang, Marquette UniversityFollow
Rajendra Rathore, Marquette UniversityFollow

Document Type

Article

Language

eng

Publication Date

7-3-2017

Publisher

Wiley

Source Publication

Chemistry- A European Journal

Source ISSN

0947-6539

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.

Comments

Accepted version. Chemistry- A European Journal, Vol. 23, No. 37 (July 2017): 8834-8838. DOI. © 2017 John Wiley & Sons, Inc. Used with permission.

Recommended Citation

Ivanov, Maxim V.; Wadumethrige, Shriya; Wang, Denan; and Rathore, Rajendra, "Unraveling the Coulombic Forces in Electronically Decoupled Bichromophoric Systems during Two Successive Electron Transfers" (2017). Chemistry Faculty Research and Publications. 894.
https://epublications.marquette.edu/chem_fac/894