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The phenomenon of nanoparticles attached to an electrode passivated by an organic layer allowing efficient electron transfer between redox species in solution and the underlying electrode to be restored has resulted in Chazalviel and Allongue proposing a theory [Chazalviel, J.-N.; Allongue, P. J. Am. Chem. Soc.2011, 133, 762–764] to explain this phenomenon. The theory suggests that with electrode-organic layer-nanoparticle constructs, high exchange current densities, compared with when the nanoparticles are absent, results in the rate of electron transfer being independent of the thickness of the organic layer until a threshold thickness is exceeded. Thereafter, the thicker the organic layer, the slower the rate of electron transfer. Herein we provide the first experimental data to support this theory using a single experimental system that can show the transition from thickness independent electron transfer kinetics …