Comparative Observation of Distinct Dynamic Stokes Shifts in Diaryl BODIPY Triads with Broadband Two-Photon Absorption.

Time-resolved evolution of excited states in the twist-conjugated chromophores is of great fundamental interest for photoluminescent applications. The four diaryl BODIPY triads modified with diverse end-cappers at 2,6-positions were investigated properly, and considerable two-photon absorption capabilities in the first biological spectral window were obtained. Fast relaxations from the initially twisted conformation to the planarized conformation in the excited state were resolved spectrally and kinetically, accompanied by the discernible phenomenon of the fluorescence dynamic Stokes shift (DSS). Along with increasing electron donating capabilities and solvent polarities, the characteristics of structural rearrangement and intramolecular charge transfer have been estimated by enhanced DSS behaviors. Especially, the blue-shifted DSS was rationalized as the sequence conversion between the planarized state and the twisted charge transfer state. A molecular-level picture for relaxation pathways in different polarities was depicted and supported by the theoretical simulations. Significant and fast structural motions in this work contribute to the excited-state dynamics and rational development of versatile BODIPY chromophores.