Photoinduced Electron Transfer and Energy Transfer Processes in a Flexible BODIPY-C Dyad.

A new donor-acceptor dyad composed of a BODIPY (4,4'-difluoro-4-bora-3a,4a-diaza--indacene) donor and a fullerene C acceptor has been synthesized and characterized. This derivative has been prepared using a clickable fullerene building block that bears an alkyne moiety and a maleimide unit. The post-functionalization of the maleimide group by a BODIPY thiol leads to a BODIPY-C dyad, leaving the alkyne moiety for further functional arrangement. On the basis of the combination of semi-empirical and density functional theory (DFT) calculations, spectroelectrochemical experiments, and steady-state and time-resolved spectroscopies, the photophysical properties of this new BODIPY-C dyad were thoroughly studied. By using semi-empirical calculations, the equilibrium of three conformations of the BODIPY-C dyad has been deduced, and their molecular orbital structures have been analyzed using DFT calculations. Two short fluorescence lifetimes were attributed to two extended conformers displaying variable donor-acceptor distances (17.5 and 20.0 Å). Additionally, the driving force for photoinduced electron transfer from the singlet excited state of BODIPY to the C moiety was calculated using redox potentials determined with electrochemical studies. Spectroelectrochemical measurements were also carried out to investigate the absorption profiles of radicals in the BODIPY-C dyad in order to assign the transient species in pump-probe experiments. Under selective photoexcitation of the BODIPY moiety, occurrences of both energy and electron transfers were demonstrated for the dyad by femtosecond and nanosecond transient absorption spectroscopies. Photoinduced electron transfer occurs in the folded conformer, while energy transfer is observed in extended conformers.