Surface-Enhanced Raman Spectroscopy and Density Functional Theory Calculations of a Rationally Designed Rhodamine with Thiol Groups at the Xanthene Ring

Rhodamines are widely used dyes in fluorescence and surface-enhanced Raman spectroscopy (SERS). The latter requires adsorption of the dye onto the surface of plasmonic nanostructures, a process which requires attractive molecule–surface interactions. Here, we report an experimental SERS and computational density functional theory (DFT) study investigating the role of thiol functionalization at the xanthene ring of the rhodamine in the adsorption onto gold nanoparticles. For this purpose, a new bisthiolated rhodamine derivative was rationally designed and synthesized via a PPh 3 /I 2 reduction route. The introduction of two thiol moieties directly at the xanthene ring provides the shortest possible distance between the molecular π-system and the metal surface for maximum SERS enhancement combined with the strong Au–S interaction for chemisorption. The comparison of experimental SERS spectra obtained from gold nanostars and a film of gold nanoparticles with results from DFT calculations (molecular electrostatic potential, normal modes) suggests adsorption via the thiol groups at the xanthene moiety.