The intermolecular reactivities of amino-substituted perchlorotriphenylmethyl radicals 1-3 were studied, with particular emphasis on electron transfer (ET) reactions. The natural fluorescence lifetimes and the rates of the electron-transfer quenching were studied with several electron donors and acceptors. Fluorescence quenching studies demonstrate the importance of the redox potentials of the ET pair on the observed steric and electronic properties.

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.