Photodimerization Kinetics of a Styrylquinoline Derivative in Langmuir–Blodgett Monolayers Monitored by Second Harmonic Generation

Abstract

To explore the influence of surface packing densities on the interfacial photochemical kinetics, the surface-selective second harmonic generation (SHG) technique was used to investigate the kinetics of two-photon induced [2 + 2] photocycloadditions of a styrylquinoline alkoxy derivative within the Langmuir–Blodgett (LB) monolayers. The laser power dependence experiment revealed that this interfacial photodimerization is a first-order reaction, which implies that the photoexcitation is the rate-limiting step. Interestingly, a comparison of photodimerization kinetics at different surface packing densities shows a nonmonotonic distribution of reaction rate constants, which can be attributed to a result of combined effects of the topochemical mechanism and steric hindrance. The atomic force microscopy measurements and theoretical calculations were also employed to help understand the [2 + 2] photocycloaddition mechanisms. The results presented in this work demonstrate that the surface packing density plays an...