Triggering the volume phase transition of core–shell Au nanorod–microgel nanocomposites with light

We have coated gold nanorods (NRs) with thermoresponsive microgel shells based on poly(N-isopropylacrylamide) (pNIPAM). We demonstrate by simultaneous laser-heating and optical extinction measurements that the Au NR cores can be simultaneously used as fast optothermal manipulators (switchers) and sensitive optical reporters of the microgel state in a fully externally controlled and reversible manner. We support our results with optical modeling based on the boundary element method and 3D numerical analysis on the temperature distribution. Briefly, we show that due to the sharp increase in refractive index resulting from the optothermally triggered microgel collapse, the longitudinal plasmon band of the coated Au NRs is significantly red-shifted. The optothermal control over the pNIPAM shell, and thereby over the optical response of the nanocomposite, is fully reversible and can be simply controlled by switching on and off a NIR heating laser. In contrast to bulk solution heating, we demonstrate that light-triggering does not compromise colloidal stability, which is of primary importance for the ultimate utilization of these types of nanocomposites as remotely controlled optomechanical actuators, for applications spanning from drug delivery to photonic crystals and nanoscale motion.