The Interplay between Solvation and Stacking of Aromatic Rings Governs Bright and Dark Sites of Benzo[g]coumarins.

Coumarins are classic, strongly polarized fluorophores with multiple applications, and significant efforts have been put into modifying their emission characteristics and elucidating their photophysics. Expecting that π-expansion of these donor-acceptor chromophores could modify their ground- and excited-state characteristics, the authors performed combined, detailed photophysical and computational studies of linearly π-expanded coumarins, that is, 8-dialkylamino-3-carboxyalkyl-benzo[g]coumarins. The investigation led to the conclusion that emission is only possible thanks to the stabilizing effect of the solvent and that breaking of the lactone ring leads to the conical intersection with the ground state and induces the radiationless decay of the electronic excitation. Aiming at the fine-tuning the excited state properties through the construction of covalently linked dye assemblies, the authors designed and synthesized a new bis(benzo[g]coumarin), built from two similar moieties that exhibit different degrees of polarization due to the electron donor at position 8: one possesses a dialkylamino, and the other a weaker amide donor. Comprehensive studies have shown that the observed weak fluorescence of the system is the result of the interplay between the solvation-induced separation of the benzo[g]coumarin moieties, which stabilizes the emitting locally excited singlet state and the π-stacking interactions, favoring their sandwiched orientation and leading to the non-emissive charge-transfer state.