The PA regions centred at ∼420 nm and ∼800 nm (clearer in Figure ) showed a spectral evolution with time consistent with the formation of charge-transfer (CT) states, as described in previous work. The negligible temporal evolution of the PB band (except for 1c at later times) is due to both photoexcited singlet and CT states exhibiting the same photobleaching, and the population of CT states from singlet excited states. The kinetics of the band at 550-570 nm exhibited a clear decay until 10 ps, but no further changes were observed after that up to 500 ps (inset Figure ), while the 770-870 nm band exhibited a clear rise due to the generation of CT states. An exponential fit to the dynamics yielded an inverse rate constant of 4-5 ps for the singlet exciton decay and 10-11 ps for the CT state generation probed at 550-570 nm and 770-870 nm in toluene, respectively (clearer in Figure ). The ps-ns TA spectra of both 1c and 1b in acetonitrile showed different spectral shapes and evolution (Fig. ) where the PB band in acetonitrile showed an immediate decay, compared to 1c in toluene. This is supported by the fast decay of the CT states (band centered at 630 nm). Table summarizes the inverse generation rates of CT states in both toluene and acetonitrile. The spectral shape and evolution are different for PyrBDP 1c in acetonitrile compared to toluene (Figures and). In acetonitrile, both molecules showed early time (after 10 ps), and faster decay of the CT states compared to the toluene solutions. 1c and 1b showed a clear difference in the spectra and dynamics of the excited states. In 1b, the CT state peaked at around 800 nm and decayed within ∼10 ns, causing the emergence of two new long-lived bands at 600 nm and 670 nm. We assigned these bands to the BODIPY triplet state based on previous reports. An exponential fit to the kinetics shown in the inset of Fig. yielded an inverse rate constant of 5.7 ns for the triplet generation and 0.7-1.2 μs for the triplet decay for 1c much longer than that observed for 1b (26.5 μs), in toluene, which are significantly shorter than those obtained in acetonitrile (∼65 μs). For 1c in toluene, we estimated a triplet yield of 58% (see the horizontal dashed line in the inset), assuming both triplet and singlet states exhibit the same absorption cross-section as reported in previous works 9a, which agrees with the one measured by relative actinometry (56-73%) using an optically matched (at pump wavelength) Rose Bengal solution in methanol as reference, see Figure and Table in the SI. A similar analysis was done for the remaining materials and solvents combination, see Figure and Table . and) TA spectra with kinetics (inset) of selected spectral region of pyrene and anthracene dyads 1b and 1c in toluene after excitation with 505 nm and 532 nm laser pulses, respectively, under inert atmosphere.