Journal of Photochemistry and Photobiology A : Chemistry
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.
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.
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