%0 Journal Article %T 4-Aminothiophenol Photodimerization Without Plasmons. %A Alessandri I %J Angew Chem Int Ed Engl %V 61 %N 28 %D Jul 2022 11 %M 35532974 %F 16.823 %R 10.1002/anie.202205013 %X 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.