Electronic and vibrational properties of meso-tetraphenylporphyrin on silver substrates

The electronic and vibrational properties of meso-tetraphenylporphyrin (mtpp) on silver substrates are investigated using UV-vis and surface-enhanced resonance Raman scattering (SERRS) spectroscopy. Whereas the vibrational signatures associated with the tetrapyrrole backbone exhibit minor variations throughout sequences of consecutively recorded SERRS spectra, the C═C stretching vibrational modes localized on the meso-phenyl moieties of mtpp exhibit noticeable intensity fluctuations, masked in the average SERRS response. We attribute the observed vibrational-state-specific blinking events to conformational changes in mtpp, namely, torsional flexibility which mediates the coupling between the π-framework of the meso-phenyls and the underlying metal substrate.