The Erratic Emission of Pyrene on Gold Nanoparticles

Gold nanoparticles functionalized with chromophores are known to present unpredictable fluorescence as a function of their structure. Odd–even effects, based on the number of methylene units of the chain to which the fluorophore is attached, and the nature of the anchoring group on the gold surface have, in the past, been suggested to be responsible for the behavior. Here we investigate the fluorescence processes of two newly synthesized pyrene derivatives bound to gold nanoparticles. Two structurally identical ligands, differing only in the nature of the anchoring group (a thiolate in one case and an amine in the other), were newly synthetized and attached to the gold nanoparticles. The same changes in the fluorescence properties, namely, a red spectral shift with a moderate increase of the quantum yield and a shortening of the excited-state lifetime, are observed in the two cases and ascribed to the proximity of the gold core. By comparison with the results reported for other pyrene derivatives, it has been possible to draw the conclusions that (i) the nature of the binding group does not affect the fluorescence properties of the fluorophores attached to the nanoparticle surface and (ii) much stronger fluorescence is observed in the case of pyrene separated from the gold by short alkyl chain. The unusual behavior is explained in simple terms of competing chain−chain and chromophore–chromophore interactions and by means of proper energy diagrams.