Abstract
Rotaxane-based mechanophores that exploit spatial separation between a luminophore and a quencher are attractive due to their high structural design flexibility, enabling high-contrast changes in fluorescence intensity. However, it remains unclear whether their quenching mechanism is predominantly governed by photoinduced electron transfer (PET) or ground-state charge-transfer (CT) complex formation. This study unveils the quenching mechanism using rotaxane mechanophores incorporating π-extended anthracene, tetracene, or pentacene. In toluene, the quenching efficiency decreases with increasing π-conjugation of the fluorophore. Steady-state and transient absorption spectroscopy clarify that the fluorescence quenching of the anthracene-containing rotaxane is primarily due to PET, with a minor contribution from CT complex formation. In contrast, no clear CT complex formation is observed for the tetracene- and pentacene-containing mechanophores. PET moderately quenches the fluorescence for the tetracene-based system, while the low PET efficiency in the pentacene-containing mechanophore results in minimal quenching. Polyurethane elastomer films containing the anthracene-based mechanophore exhibit a significant increase in fluorescence intensity upon mechanical deformation. In contrast, almost no activation is observed for the pentacene-based mechanophore embedded in polyurethane. These findings clarify that PET is the primary quenching mechanism in rotaxane-based mechanochromic mechanophores, offering valuable insights for the future design of supramolecular mechanophores.