Switching of the Triplet Excited State of Styryl 2,6-Diiodo-Bodipy and Its Application in Acid-Activatable Singlet Oxygen Photosensitizing

IodoBodipy-styrylBodipy dyads triplet photosensitizers were prepared (B-1 and B-2) which contain acid-responsive moiety. Both compounds show broadband visible light absorption, due to the resonance energy transfer (RET) between the two different visible light-harvesting Bodipy units. The photophysical properties of the dyads were studied with steady-state and nanosecond time-resolved transient absorption spectroscopy. The production of triplet excited state is switched ON or OFF by protonation/deprotonation of the amino group in the dyads. In the neutral form, the excited state is short-lived (<10 ns) and no singlet oxygen ((1)O2) photosensitizing was observed. Upon protonation, a long-lived triplet excited state was observed (τT = 3.1 μs) and the (1)O2 quantum yield (ΦΔ) is up to 73.8%. The energy levels of the components of the dyads were changed upon protonation and this energy level tuning exerts significant influence on the triplet state property of the dyad. Acid-activated shuffling of the localization of the triplet excited state between two components of a dyad was observed. Furthermore, we observed a rare example that a chromophore giving shorter absorption wavelength is acting as the singlet energy acceptor in RET. The experimental results were rationalized by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations.