Journal of Physical Chemistry C
Journal of Physical Chemistry C
5 years ago

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

Photodimerization Kinetics of a Styrylquinoline Derivative in Langmuir–Blodgett Monolayers Monitored by Second Harmonic Generation
Zhou Lu, Li Zhang, Yuan Guo, Yu Xie, Minghua Liu, Yingxue Ma, Lu Lin, Zhenggang Lan
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 important role in regulating the interfacial photoreactions within the LB monolayers composed of the conjugated aromatic molecular systems.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b08409

DOI: 10.1021/acs.jpcc.7b08409

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