Combined Covalent and Supramolecular Polymerization to Reinforce Perylenebisimide Photosynthetic "Quantasomes".

PSII-inspired quantasomes have emerged as promising artificial photosystems evolving oxygen from water due to their integrated multi-chromophore asset, hierarchical architecture, and efficient light-harvesting capabilities. In this study, we adopt a combined covalent and supramolecular strategy by implementing a poly-styrene backbone that reinforces proximity and pairing between adjacent perylenebisimide (PBI) quantasome units. The covalent fixation of the quantasome network results in a significant enhancement of the photoelectrocatalytic performance on engineered IO-ITO photoanodes, with up to 290 % photocurrent increase (J up to 100 μA cm, λ >450 nm, applied bias <1.23 V vs RHE, F.E.O >80 %) compared to the non-polymerized analog. Moreover, the direct PBI-quantasome polymerization on the photoanode surface was performed by light irradiation of the radical initiator 2,2'-Azobis(2-methylpropionamidine), improving the photoelectrode robustness under high solar irradiance (>8 suns) and limiting the photocurrent loss (<20 %) at 1.52 V vs RHE compared to the non-polymerized system.