The Prevalence of Anions at Plasmonic Nanojunctions: A Closer Look at p-Nitrothiophenol

We revisit the reductive coupling of p-nitrothiophenol (NTP) to form dimercaptoazobenzene (DMAB), herein monitored through gap-mode tip-enhanced Raman spectroscopy (TERS) and nanoimaging. We employ a plasmonic Au probe (100 nm diameter at its apex) illuminated with a 633 nm laser source (50 μW/μm² at the sample position) to image an NTP-coated faceted silver nanoparticle (∼70 nm diameter). A detailed analysis of the recorded spectra reveals that anionic NTP species contribute to the recorded spectral images, in addition to the more thoroughly described DMAB product. Notably, the signatures of the anions are more pronounced than those of the DMAB product under our present experimental conditions. Our results thus demonstrate that anions and their spectral signatures must be considered in the analysis of plasmon-enhanced optical spectra and images.