Photoinduced Chirality Switching of Metal-Inorganic Plasmonic Nanostructures.

Chiral plasmonic nanodevices whose handedness can be switched reversibly between right and left by external stimulation have attracted much attention. However, they require delicate DNA nanostructures and/or continuous external stimulation. In this study, those issues are addressed by using metal-inorganic nanostructures and photoinduced reversible redox reactions at the nanostructures, namely, site-selective oxidation due to plasmon-induced charge separation under circularly polarized visible light (CPL) and reduction by UV-induced TiO ₂ photocatalysis. We irradiate gold nanorods (AuNRs) supported on TiO ₂ with right- or left-CPL to generate electric fields with chiral distribution around each AuNR and to deposit PbO ₂ at the sites where the electric fields are localized, for fixing the chirality to the AuNR. The nanostructures thus prepared exhibit circular dichroism (CD) based on longitudinal and transverse plasmon modes of the AuNRs. Their chirality given by right-CPL (or left-CPL) is locked until PbO ₂ is rereduced under UV light. After unlocking by UV, the chirality can be switched by left-CPL (or right-CPL) irradiation, resulting in reversed CD signals and locking the switch again. The handedness of the chiral plasmonic nanodevice can be switched reversibly and repeatedly.