Charge-transfer or excimeric state? Exploring the nature of the excited state in cofacially arrayed polyfluorene derivatives
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, A., Ivanova, L., Wang, D., Navale, T., Abdelwahed, S., Ivanov, M., Lindeman, S., Rathore, R., & Reid, S. (2019). Charge-transfer or excimeric state? Exploring the nature of the excited state in cofacially arrayed polyfluorene derivatives. Retrieved from https://digitalcommons.pvamu.edu/chemistry-physics-facpubs/2