Real-Time Observation of Ultrafast Concerted Dynamics between Energy and Chirality Transfer by Femtosecond Time-Resolved Circular Polarization Luminescence Spectroscopy

Elucidating the underlying mechanism of effective chirality and energy transfer processes observed in biological assemblies has cross-disciplinary significance, and it is of special interest in the fields of chemistry and biology due to the pivotal role of chirality in life. Challenges in the field include how to achieve real-time monitoring of the chirality and energy transfer dynamics simultaneously, as well as how to distinguish whether these processes take place in the ground or excited state. Herein, we achieve the first attempt at real-time observation of the concerted ultrafast dynamics between the Förster resonance energy transfer (FRET) and the generation of circularly polarized luminescence (CPL) in the excited state in near-infrared CPL supramolecular nanofibers (SNFs) by using femtosecond time-resolved circularly polarized luminescence (fs-TRCPL) spectroscopy. Our findings reveal a cooperative interplay between FRET and CPL emission, unfolding over time scales from several to hundreds of picoseconds. Notably, we identify that the pivotal mechanism leading to a 0.045 g_lum value in SNFs is the difference in the FRET rates between left- and right-handed circularly polarized emission channels, which is a reason beyond the well-known relationship of the electronic and magnetic dipoles. Our results not only shed light on the understanding of the chirality transfer mechanism in the excited states but also pave the road for the development of novel CPL materials in the future.