Environment-sensitive fluorescence of COT-fused perylene bisimide based on symmetry-breaking charge separation

Flexible and aromatic photofunctional system (FLAP) is composed of flapping rigid aromatic wings fused with a flexible 8π ring at the center such as cyclooctatetraene (COT). A series of FLAP have been actively studied for the interesting dynamic behaviors. Here, we synthesized a new flapping molecule bearing naphtho-perylenebisimide wings (NPBI-FLAP), in which two perylene units are arranged side by side. As a reference compound, we also prepared COT-fused NPBI (NPBI-COT) that contains only single perylene unit. In both compounds, inherent strong fluorescence of the NPBI moiety is almost quenched and the FL lifetime becomes much shortened in highly polar solvents (acetone and DMF). Through the analyses of environment-sensitive fluorescence, electrochemical reduction/oxidation, and femtosecond transient absorption, the fluorescence quenching behavior was attributed to rapid symmetry-breaking charge separation (SB-CS) for NPBI-FLAP and to intramolecular charge transfer (ICT) for NPBI-COT. Most of the excited species of these compounds decay with the bent geometry, which is in contrast with the excited-state planarization behavior of a previously reported COT-fused peryleneimides with the double-headed arrangement of the perylene moieties. These results indicate that changing the fusion manners between COT and other π skeletons offers new functional molecules with distinct dynamics.