Time-resolved vibrational spectroscopic study of molecular nanoaggregate photocatalysts.

The controlled aggregation of organic chromophores into supramolecular structures offers a way to control and tune photocatalytic activity. However, the underlying mechanisms of charge transfer and accumulation are still unclear. Time-resolved vibrational spectroscopy is a powerful structural probe for studying photogenerated intermediates. Here, we employ time-resolved infrared (TRIR) spectroscopy to study CNP (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9-carbazol-3-yl)pyridine-3,5-dicarbonitrile) and its supramolecular aggregates. We show that excitation of the charge transfer (CT) band of semi-crystalline nanofibers (CNP-f) gives rise to long-lived delocalised polarons, which form within the instrument response timescale. By contrast the CNP nanospheres (CNP-s) give rise to a shorter lived polaron that appears to have a greater degree of localization. CNP-f and CNP-s are known to show markedly different levels of photocatalytic activity for hydrogen and hydrogen peroxide formation which are rationalised owing to these differences in photodynamics immediately following photon absorption.