Selective population of triplet excited states in heavy-atom-free BODIPY-C₆₀ based molecular assemblies

Photophysical studies on a BODIPY-fullerene-distyryl BODIPY triad (BDP-C₆₀-DSBDP) and its reference dyads (BODIPY-fullerene; BDP-C₆₀ and distyryl BODIPY-fullerene; DSBDP-C₆₀) are presented herein. In the triad, the association of the two chromophore units linked by a fullerene moiety leads to strong near UV-Visible light absorption from 300 to 700 nm. The triplet-excited state was observed upon visible excitation in all these assemblies, and shown to be localized on the C₆₀ or BODIPY moieties. Using quantitative nanosecond transient absorption, we provide a complete investigation on the lifetime and formation quantum yield of the triplet-excited state. In the BDP-C₆₀ dyad, the triplet excited state of C₆₀ (τ = 7 ± 1 μs) was obtained with a quantum yield of 40 ± 8%. For the DSBDP-C₆₀ dyad and BDP-C₆₀-DSBDP triad, a longer-lived triplet excited state with a lifetime of around 250 ± 20 μs centered on the DSBDP moiety was formed, with respective quantum yields of 37 ± 8 and 20 ± 4%. Triplet-triplet annihilation up-conversion is characterized in the BDP-C₆₀ dyad and the bichromophoric triad in the presence of perylene and DSBDP-monomer as respective annihilators. The photo-induced formation of a long-lived ³DSBDP* in the triad coupled with panchromatic light absorption offers potential applications as a heavy-atom-free organic triplet photosensitizer.