Electronic Relaxation Dynamics in 2-Quinolinones with Extended Conjugation

The 2-quinolinone family of molecules, also known as carbostyrils, have been proposed as light absorbing donor molecules in energy transfer based sensing schemes and as possible photocatalysts. Both of these applications make use of electronic excited states, but the photophysics of 2-quinolinones have not yet been examined closely. This study applies static and dynamic spectroscopy, with supporting density functional theory calculations, to reveal the electronic relaxation dynamics of a family of five 2-quinolinones with extended conjugated rings. These modifications lead to red-shifted absorbance and emission maxima, relative to unmodified 2-quinolinone. Optical excitation of these molecules with near UV light resulted in transitions with strong π → π* and HOMO → LUMO character. Time-correlated single photon counting measurements yielded fluorescence lifetimes ranging from 849.3 (±0.6) ps to 4.586 (±0.002) ns. Transient absorption spectroscopy revealed relaxation dynamics of the S₁ excited state formed by photoexcitation at 350 nm, along with formation of a long-lived signal assigned as excited state absorption by a triplet excited state. Vibrational relaxation in the S₁ state was also characterized in some compounds. Overlapping signals of S₁ decay and triplet growth in the transient absorption data set could not be fully disentangled. These results demonstrate a highly competitive relaxation scheme following multiple simultaneous pathways, a promising situation for establishing chemical control of electronic relaxation in the 2-quinolinone family.