Solvation Controlled Excited-State Planarization in a Push-Pull Pyrene Dye

摘要

The excited-state deactivation pathway of the push-pull pyrene derivative (EPP), a molecule emitting bright red fluorescence, has been studied in several solvents using quantum chemical calculations, femtosecond time-resolved fluorescence up-conversion spectroscopy, and femtosecond transient absorption spectra (fs-TA). From the steady-state spectra, EPP has shown a strong negatively solvatochromic behavior of the absorption spectra and non-solvatochromic emission spectra, revealing the decreased dipole moment upon excitation. Femtosecond upconversion measurements have shown interesting rise-decay kinetics at the red emission side and fs-TA spectra also feature the SE (stimulated emission) formed and new ESA (excited-state absorption) developed in all investigated solvents. The careful analysis of the data gathered from fluorescence up-conversion and fs-TA spectra, supported by DFT quantum chemical calculations and temperature-dependent fluorescence measurements, unambiguously pointed out the excited-state relaxation pathway of EPP is controlled by solvent stabilized planar intramolecular charge transfer (PICT) dynamics. This finding confirms the surrounding solvents as a significant factor that affects the rate of excited-state conformation changes.