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The influence of core size on electronic coupling in shell-core nanoparticles: gold clusters capped with pyrenoxylalkylthiolate.

The mean size of the metallic core of monolayer-protected gold clusters densely capped with 9-(1-pyrenoxyl)octane-1-thiol or 1-dodecanethiol can be adjusted by controlling the thiol/HAuCl4 ratio during synthesis. Upon reduction of tetrachloroaurate by NaBH4, lower mean metal core diameters were attained in those composites prepared from mixtures with higher thiol/Au ratios. The efficiency of electronic coupling between the core metal cluster and pyrenyl groups appended as an outer shell in this size-graded family was studied by absorption and fluorescence spectroscopy. The observed emission intensity from the bound fluorophores is independent of the gold core size.