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Arrays of Ag and Au Nanoparticles with Terpyridine- and Thiophene-Based Ligands: Morphology and Optical Responses
journal contribution
posted on 2017-04-10, 00:00 authored by Markéta Prusková, Veronika Sutrová, Miroslav Šlouf, Blanka Vlčková, Jiří Vohlídal, Ivana ŠloufováThe
assembly of Ag and Au nanoparticles (NPs) into nanoparticulate
arrays mediated by terpyridine (tpy), 4′-(2-thienyl)terpyridine
(T-tpy), and short α,ω-bis(tpy)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 Ags0 and Aus0 adsorption sites on metal NPs to antibonding orbitals of the adsorbates
have been identified for Ag/tpy, Ag/T-tpy, Au/tpy,
and Au/T-tpy nanoparticulate arrays. Although the
surface–adsorbate complexes displaying a photoinduced CT are
known for Ag NPs, the Aus0 surface complexes with this CT are newly reported. Bis(tpy)oligothiophenes were found to be attached to both Ag
and Au NPs via the tpy 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 Ags0 as
well as Aus0 surface complex formation has not been obtained.
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Keywords
excitation wavelengthnanoparticulate arraysmetal NPsantibonding orbitalssurface plasmon excitationsSPE spectrainterparticle distancesThiophene-Based LigandsSERSphotoinduced CTinterparticle linkersNP hydrosolmolecules actsurface plasmon extinction0 surface0 adsorption sitesPhotoinduced charge transferTEMOptical Responsesinterparticle distancetransmission electron microscopyNP islandsoligomers moleculesmarker band evidenceAg NPsimage analysis0 surface complexestpy
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