Promoted Charge Separation and Long-Lived Charge-Separated State in Porphyrin-Viologen Dyad Nanoparticles

[Image: see text] Developing light-harvesting systems with efficient photoinduced charge separation and long-lived charge-separated (CS) state is desirable but still challenging. In this study, we designed a zinc porphyrin photosensitizer covalently linked with viologen (ZnP-V) that can be prepared into nanoparticles in aqueous solution. In DMF solution, the monomeric ZnP-V dyads show no electron transfer between the ZnP and viologen units. In contrast, the ZnP-V nanoparticles in aqueous solution show fast charge separation with a CS state lifetime of up to 4.3 ms. This can be attributed to charge hopping induced by aggregation or distance modification between the donor and acceptor induced by electronic interaction. Nevertheless, the lifetime of the CS state is orders of magnitude longer than for molecular aggregates reported previously. The ZnP-V nanoparticles show enhanced photocatalytic hydrogen production as compared to the ZnP nanoparticles and still hold promise for other applications such as photovoltaic devices and photoredox catalysis.