Rigid, Branched Porphyrin Antennas: Control over Cascades of Unidirectional Energy Funneling and Charge Transfer.

Porphyrin arrays consisting of three peripheral Zinc porphyrins (ZnPs) and a central free base porphyrin (H2P)-all rigidly linked to each other-serve as light-harvesting antennas as well as electron donors and are flexibly coupled to an electron-accepting C60 to realize the unidirectional flow of (i) excited-state energy from the ZnPs at the periphery to the H2P, (ii) electrons to C60, and (iii) holes to H2P and, subsequently, to ZnP. Dynamics following photoexcitation are elucidated by time-resolved transient absorption measurements on the femto-, pico-, nano-, and microsecond time scales and are examined by multiwavelength as well as target analyses. Hereby, full control over the charge shift between H2P and ZnP to convert the (ZnP)3-H2P•+-C60•- charge-separated state into (ZnP)3•+-H2P-C60•- charge-separated state is enabled by the solvent polarity: It is deactivated/switched-off in apolar toluene, while in polar benzonitrile it is activated/switched-on. Activating/switching impacts the recovery of the ground state via charge recombination rates, which differ by up to 2 orders of magnitude. All charge-separated states lead to the repopulation of the ground state with dynamics that are placed in the inverted region of the Marcus parabola.