Insights into Plasmon-Induced Dimerization of Rhodanine-A Surface-Enhanced Raman Scattering Study

Plasmon-mediated chemical reactions (PMCRs) have attracted considerable interest in recent times. The PMCR initiated by hot carriers is known to be influenced by the type of metals and the excitation wavelength. Herein, we have carried out the surface-enhanced Raman scattering (SERS) investigation of rhodanine (Rd), an important pharmacologically active heterocyclic compound, adsorbed on silver and gold nanoparticles (AgNP and AuNP) using 514.5 and 632.8 nm lasers. The prominent Raman band at 1566 cm^-1 observed in the SERS spectra is attributed to the characteristic ν(C═C) stretching vibration of the Rd dimer and not of Rd tautomers. The chemical transformation of Rd to Rd dimer on metal surfaces is plausibly triggered by the indirect transfer of energetic hot electrons generated during the non-radiative decay of plasmon. The mechanism involved in the dimerization of Rd via the indirect transfer of hot electrons is also presented. The effect of wavelength on the dimerization of Rd is also observed on the AgNP surface, which indicates that the dimerization occurs more efficiently on the AgNP surface with excitation at 514.5 nm wavelength.