The influence of the length of a
self-assembled monolayer (SAM) linker on the
electrochemical performance of electrode-linker-gold
nanoparticle molecular constructs is investigated.
Electrodes were first modified with amino-1-alkanethiols of four different lengths (C = 2, 6, 8, and 11). The SAM showed progressively greater blocking ability to
ruthenium hexamine as the length of the
alkyl chain increased to the point where no significant Faradaic peak was observed for the amino-1-undecanethiol SAM. Upon the attachment of
gold nanoparticles, distinct Faradaic
electrochemistry of the
ruthenium hexamine was observed for all four length SAMs with the
electrochemistry being similar to that observed on a bare
electrode. The charge transfer resistance to this Faradaic process was observed to be insensitive to the length of the intervening SAM, indicating it is
electron transfer between the redox species and the
nanoparticles, rather than tunneling across the SAM, which is the
rate-limiting step. Some comments on the mechanism of charge transfer are provided. When forming multilayers of the linker-nanoparticle constructs, fabricated in a stepwise manner, whenever the
distal species was the SAM the Faradaic process was blocked and whenever it was the
nanoparticle a distinct Faradaic process was observed. With up to five layers of linker-nanoparticles, there was little increase in charge transfer resistance and again the charge transfer resistance was insensitive to the length of the linker.
