Plasmonic nanoparticle networks formed using iron porphyrin molecular bridges

The adsorption orientation of the iron(III) tetrakis(1-methyl-4-pyridyl)porphine (FeTMPyP) μ-oxo-bridged dimer species located in the inter-particle gap of solid gold nanosphere (SGN) and hollow gold nanosphere (HGN) networks was studied using a combination of linear extinction and surface-enhanced Raman Scattering (SERS) measurements. Nanoparticle aggregation was accomplished by μM additions of iron porphyrin to the colloidal SGN and HGN solutions. Aggregation was monitored by measuring the UV-Visible-NIR extinction spectra of the nanoparticle systems; a broadened and red-shifted localized surface plasmon resonance (LSPR), relative to the LSPR of the isolated nanoparticles, indicated aggregate formation. In conjunction with the LSPR extinction measurements, wavelength-dependent SERS measurements were used to determine the orientation of the FeTMPyP with respect to the SGN and HGN surfaces.