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.

Comments

Accepted version. Journal of Photochemistry and Photobiology A : Chemistry, Vol. 371 (April 2019): 125-130. DOI. © 2019 Elsevier. Used with permission.

Available for download on Thursday, April 01, 2021

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