Photoinduced Fano Resonances between Quantum Confined Nanocrystals and Adsorbed Molecular Catalysts.

Interaction of surface adsorbate vibration and intraband electron absorption in nanocrystals has been reported to affect the photophysical properties of both nanocrystals and surface adsorbates and may affect the performance of hybrid photocatalysts composed of semiconductor nanocrystals and molecular catalysts. Here, by combining ultrafast transient visible and IR spectroscopic measurements, we report the observation of Fano resonances between the intraband transition of the photogenerated electrons in CdS and CdSe nanocrystals and CO stretching vibrational modes of adsorbed molecular catalysts, [Fe ₂ (cbdt)(CO) ₆ ] (FeFe; cbdt = 1-carboxyl-benzene-2,3-dithiolate), a molecular mimic for the active site of FeFe-hydrogenase. The occurrence of Fano resonances is independent of nanocrystal types (rods vs dots) or charge transfer character between the nanocrystal and FeFe, and is likely a general feature of nanocrystal and molecular catalyst hybrid systems. These results provide new insights into the fundamental interactions in these hybrid assemblies for artificial photosynthesis.