The Role of Structural Flexibility in Plasmon‐Driven Coupling Reactions: Kinetic Limitations in the Dimerization of Nitro‐Benzenes

The plasmon‐driven dimerization of 4‐nitrothiophenol (4NTP) to 4‐4′‐dimercaptoazobenzene (DMAB) is a testbed for understanding bimolecular photoreactions enhanced by nanoscale metals, in particular, regarding the relevance of electron transfer and heat transfer from the metal to the molecule. By adding a methylene group between the thiol bond and the nitrophenyl, structural flexibility is added to the reactant molecule. Time‐resolved...