Arrays of Ag and Au Nanoparticles with Terpyridine- and Thiophene-Based Ligands: Morphology and Optical Responses

The assembly of Ag and Au nanoparticles (NPs) into nanoparticulate arrays mediated by terpyridine (tpy), 4′-(2-thienyl)­terpyridine (T-<i>tpy</i>), and short α,ω-bis­(<i>tpy</i>)­oligothiophene ligands has been accomplished at the interface between the Ag or Au NP hydrosol and a solution of the molecular species in dichloromethane. The relationship between the morphology and the optical responses of the arrays has been investigated by advanced methods of TEM (transmission electron microscopy) image analysis and surface plasmon extinction (SPE) spectra. It has been established that the size of islands of closely spaced NPs rather than the average interparticle distance affects the extent of delocalization of the surface plasmon excitations and thus also the SPE spectra. Furthermore, the structure of surface–adsorbate complexes formed in these arrays has been investigated by SERS spectral measurements carried out as a function of the excitation wavelength. Photoinduced charge transfer (CT) transitions from the neutral Ag<sub>s</sub><sup>0</sup> and Au<sub>s</sub><sup>0</sup> adsorption sites on metal NPs to antibonding orbitals of the adsorbates have been identified for Ag/tpy, Ag/T-<i>tpy</i>, Au/tpy, and Au/T-<i>tpy</i> nanoparticulate arrays. Although the surface–adsorbate complexes displaying a photoinduced CT are known for Ag NPs, the Au<sub>s</sub><sup>0</sup> surface complexes with this CT are newly reported. Bis­(<i>tpy</i>)­oligothiophenes were found to be attached to both Ag and Au NPs via the <i>tpy</i> group(s). The match between the interparticle distances within the NP islands and the lengths of the oligomers molecules indicates that the molecules act as interparticle linkers. In this case, unequivocal spectral marker band evidence of the Ag<sub>s</sub><sup>0</sup> as well as Au<sub>s</sub><sup>0</sup> surface complex formation has not been obtained.