Packing-induced selectivity switching in molecular nanoparticle photocatalysts for hydrogen and hydrogen peroxide production

Molecular packing controls optoelectronic properties in organic molecular nanomaterials. Here we report a donor–acceptor organic molecule (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9 H -carbazol-3-yl)pyridine-3,5-dicarbonitrile) that exhibits two aggregate states in aqueous dispersions: amorphous nanospheres and ordered nanofibres with π – π molecular stacking. The nanofibres promote sacrificial photocatalytic H 2 production (31.85 mmol g −1 h −1 ) while the nanospheres produce hydrogen peroxide (H 2 O 2 ) (3.20 mmol g −1 h −1 in the presence of O 2 ). This is the first example of an organic photocatalyst that can be directed to produce these two different solar fuels simply by changing the molecular packing. These different packings affect energy band levels, the extent of excited state delocalization, the excited state dynamics, charge transfer to O 2 and the light absorption profile. We use a combination of structural and photophysical measurements to understand how this influences photocatalytic selectivity. This illustrates the potential to achieve multiple photocatalytic functionalities with a single organic molecule by engineering nanomorphology and solid-state packing. A donor–acceptor molecule assembles with different molecular packing to form photocatalysts which selectively produce either H 2 or H 2 O 2 , depending on the aggregate structure, a proof-of-concept of photoactivity polymorphism.