Unraveling the Mechanisms of On-Surface Photoinduced Reaction with Polarized Light Excitations

On-surface reaction has been shown as a powerful strategy to achieve atomically precise nanostructures. Numerous reactions have been realized on surfaces with thermal annealing as the primary excitation. In contrast, far fewer reactions have been triggered by light on surfaces despite its advantages due to the nonthermal process. This is possibly ascribed to our limited understanding on the excitation mechanisms of on-surface photoinduced reactions. In this work, we have studied the photoinduced debrominated coupling by using a linearly polarized light. We successfully achieved the reaction with no annealing process and obtained oligomers as the primary reaction products, which is in contrast with the formation of polymers with traditional thermal treatments. By exploring the dependence of reaction yield on the angle of incidence, we demonstrate an experimental method that can provide fundamental insights. The comparison with the theoretical approximation suggests indirect hot carrier excitation as the leading excitation mechanism. Our results not only provide fundamental insight into the surface photochemical reactions but also set the basis for harnessing light to construct unconventional nanomaterials.