Document Type
Article
Language
eng
Publication Date
4-2019
Publisher
Elsevier
Source Publication
Journal of Photochemistry and Photobiology A : Chemistry
Source ISSN
1010-6030
Abstract
It is well known that upon electronic excitation various π-stacked dimers readily exhibit excimer formation, facilitated by a perfect sandwich-like arrangement between the chromophores. However, it is unclear whether such a dimer is also capable of electron transfer upon excitation, if a strong electron-donating group is covalently attached. In this work, we probe the nature of the excited state in a series of cofacially arrayed polyfluorene derivatives with electron-rich aromatic donor attached via a methylene linker. Our studies show that in all cases excimer formation is energetically favorable, and promotion of a charge-transfer state in such systems is possible but requires a free energy for electron transfer far exceeding 1 V. These findings shed light on important design principles for molecular scaffolds capable of stabilizing both excimeric and charge-transfer states upon their excitation.
Recommended Citation
Abzhanova, Ainur; Ivanova, Lena V.; Wang, Denan; Navale, Tushar S.; Abdelwahed, Sameh H.; Ivanov, Maxim Vadimovich; Lindeman, Sergey V.; Rathore, Rajendra; and Reid, Scott A., "Charge-Transfer or Excimeric State? Exploring the Nature of The Excited State in Cofacially Arrayed Polyfluorene Derivatives" (2019). Chemistry Faculty Research and Publications. 997.
https://epublications.marquette.edu/chem_fac/997
Comments
Accepted version. Journal of Photochemistry and Photobiology A : Chemistry, Vol. 371 (April 2019): 125-130. DOI. © 2019 Elsevier. Used with permission.