Understanding the photophysical properties of coumarin-based Pluronic-silica (PluS) nanoparticles by means of time-resolved emission spectroscopy and accurate TDDFT/stochastic calculations.

The photophysical properties of two 7-aminocoumarin molecules with flexible and rigid alkyl moieties at the 7-nitrogen atom have been investigated in ethanol and in Pluronic-silica nanoparticles (PluS NPs) by means of time-resolved emission spectroscopy (TRES) and time-dependent density functional theory (TDDFT). Although the two coumarin derivatives have very different photophysical properties in solution, they show quite similar photophysical behaviour when embedded into the NPs, where an increase in the fluorescence quantum yield of about 10 times was observed for the more flexible molecule. TDDFT calculations employing long-range corrected functionals and with proper account of environmental effects reveal that the formation of an accessible twisted-intramolecular charge transfer state (TICT) is possible for 7-aminocoumarin molecules with flexible alkyl groups in fluid solution, where a conical intersection between the S1 and S0 states is observed at a dihedral angle of about 80°. The excited state dynamics of the population density of this reaction coordinate in ethanol and in silica NPs investigated through the resolution of a generalized Smoulochowsky equation shows that this deactivation mechanism is drastically hampered in a silica matrix, in good agreement with experimental evidence. Steady state and time resolved measurements also suggest that at high concentration for both the dyes intermolecular interactions into the silica matrix lead to fluorescence quenching. TDDFT/PCM calculations clearly indicate that the strong quenching and red shift observed is imputable to the formation of excimers with CT character after absorption of the monomeric species.