Green and far-red-light induced electron injection from perylene bisimide to wide bandgap semiconductor nanocrystals with stepwise two-photon absorption process

Stepwise two-photon absorption (2PA) processes are becoming an important technique because it can achieve high reductive photochemical reactions with visible and near infrared light and intensity-gated high spatiotemporal selectivity with much lower power thresholds than those of the simultaneous 2PA. However, excited states generated by stepwise 2PA (higher excited states and excited states of transient species) are so short-lived that the efficiency for the stepwise 2PA induced photochemical reactions is usually quite low, which limits the versatility for this technique. Here, we demonstrated that the electron of the higher excited state can be efficiently extracted in a nanohybrid of organic molecules and wide bandgap semiconductor nanocrystals (NCs). Using perylene bisimide (PBI)-coordinated CdS NCs as a model compound, we demonstrated that the electron of the higher excited state of PBI generated by stepwise 2PA can be extracted to the conduction band of CdS NCs with a quantum yield of ∼0.5-0.7. Moreover, the extracted electron survives at the conduction band of CdS NCs over nanoseconds, which is more than hundred times longer than the lifetime of the S2 state of PBI. This method can be applied to other organic molecules and larger wide bandgap semiconductors, and therefore, will expand the versatility for the photochemical reactions utilizing the short-lived excited states.