Abstract
The nonradiative decay of four dipolar fluorenone derivatives (FODs) was systematically investigated using steady state and time-resolved UV-vis absorption and fluorescence measurements combined with cyclic voltammetry. Analysis of the frontier orbital localization of the global minimum geometry and the vertical transitions was carried out from DFT calculations. The first singlet excited state was found to be π-π* in all derivatives regardless of the polarity of the solvent. Charge separation/recombination dominates the singlet excited state deactivation for carbazole-containing FODs. Intersystem crossing (ISC) operates exclusively in the 3,6-disubstituted variants as evidenced by phosphorescence experiments. In the case of CPAFO36, ISC competes disadvantageously with CT deactivation.
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