4-Aminothiophenol Photodimerization Without Plasmons**

The photodimerization of 4-aminothiophenol (PATP) into 4,4 '-dimercaptobenzene (DMAB) has been extensively utilized as a paradigm reaction to probe the role of surface plasmons in nanoparticle-mediated light-driven processes. Here I report the first observation of the PATP-to-DMAB photoreaction in the absence of any plasmonic mediators. The reaction was observed to occur with different kinetics either for PATP adsorbed on non-plasmonic nanoparticles (TiO2, ZnO, SiO2) or deposited as macroscopic droplets. Confocal microRaman spectroscopy enabled to investigate the reaction progress in different plasmon-free contexts, either aerobic or anaerobic, suggesting a new interpretation of the photodimerization process, based on direct laser-induced activation of singlet oxygen species. These results provide new insights in light-driven redox processes, elucidating the role of sample morphology, light and oxygen.