Insights into the effect of ketylimine, aldimine, and vinylene group attachment and regiosubstitution on the fluorescence deactivation of fluorene

The spectroscopic and electrochemical properties of a 9-substituted fluorene ketylimine (3) were investigated and compared with those of its vinylene analogue (4) to determine the origins of the quenched fluorescence of these compounds. The predominate mode of singlet excited state deactivation of the heteroatomic fluorene was found to be internal conversion involving bond rotation. Meanwhile, its carbon counterpart was found to undergo deactivation preferentially by intersystem crossing to form its triplet, which was confirmed by laser flash photolysis. Both 3 and 4 quenched the fluorescence of fluorene with diffusion-controlled rate constants, implying that the singlet excited states of 3 and 4 are also quenched by intramolecular photoinduced electron transfer (PET). This deactivation mode was found to be exergonically favorable (–90 kJ/mol for 3 and –81 kJ/mol for 4) according to the Rehm–Weller equation. The position of the heteroatomic bond on the fluorene moiety was further found to influence the singlet excited state deactivation pathway. The 2-substituted regioisomer decayed predominately by intramolecular PET and its fluorescence can be restored by acid protonation. Conversely, the PET mechanism is a minor deactivation mode for the 9-substituted fluorene derivative and its fluorescence can be enhanced by suppressing bond rotational modes, possible at low temperature and potentially in thin films.