Temperature
Dependence of Solid-State Electron Exchanges
of Mixed-Valent Ferrocenated Au Monolayer-Protected Clusters
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Abstract
Electron transfers (ETs) in mixed-valent
ferrocene/ferrocenium
materials are ordinarily facile. In contrast, the presence of ∼1:1
mixed-valent ferrocenated thiolates in the organothiolate ligand shells
of <2 nm diameter Au<sub>225</sub>, Au<sub>144</sub>, and Au<sub>25</sub> monolayer-protected clusters (MPCs) exerts a retarding effect
on ET between them at and below room temperature. Near room temperature,
in dry samples, bimolecular rate constants for ET between organothiolate-ligated
MPCs are diminished by the addition of ferrocenated ligands to their
ligand shells. At lower temperatures (down to ∼77 K), the thermally
activated (Arrhenius) ET process dissipates, and the ET rates become
temperature-independent. Among the Au<sub>225</sub>, Au<sub>144</sub>, and Au<sub>25</sub> MPCs, the temperature-independent ET rates
fall in the same order as at ambient temperatures: Au<sub>225</sub> > Au<sub>144</sub> > Au<sub>25</sub>. The MPC ET activation
energy
barriers are little changed by the presence of ferrocenated ligands
and are primarily determined by the Au nanoparticle core size