NIR-FT-SERS of 4″-trimethylsilylethylsulfanyl-4,4′-di(phenyleneethynylene)benzenethiol on Au nanospheres

Oligo(phenyleneethynylene) (OPE) compounds have been identified as promising molecular electronic bridges. Self-assembled monolayers of 4″-trimethylsilylethylsulfanyl-4,4′-phenyleneethynylenebenzene thiol (OPE′) on Au were characterized by surface-enhanced Raman scattering (SERS). The FT-Raman spectrum of OPE′ shows three C–S bands at 834, 1086, and 1131 cm−1. From the FT-Raman to the SERS spectra, the 1086 cm−1 band exhibits a 9 cm−1 red shift. Chemisorption of OPE′ to the gold surface occurs via oxidative cleavage of the disulfide bond and the formation of the Au–S bond. The Au–S vibration is visible in the SERS spectra at 257 cm−1. Peaks due to the S–S and S–H stretch are observed at 544 and 2519 cm−1, respectively, in the FT spectrum, but are unobserved in the surface-enhanced spectra. The C–H stretching region (2700–3350 cm−1) in the spectrum of neat OPE′ shows three distinct bands, whereas the SERS spectra show a single broad band. Assignments of vibrational bands were based on DFT calculations performed at the B3LYP level with good agreement between theoretical and experimental values. An average percent difference of 2.52 was obtained for the non-CH stretching frequencies.