We
have been able to “tune” the electrocatalytic
activity of iron phthalocyanine (FePc) and iron hexadodecachlorophthalocyanine
(16(Cl)FePc) for the oxygen reduction reaction (ORR) by manipulating
the “pull effect” of pyridinium molecules axially bounded
to the phthalocyanine complexes (FePcs). These axial ligands play
both the role of molecular anchors and also of molecular wires. The
axial ligands also affect the reactivity of the Fe metal center in
the phthalocyanine. The “pull effect” originates from
the positive charge located on the pyridinium core. We have explored
the influence of the core positions (Up or Down), in two structural
pyridiniums isomers on the activity of FePc and 16(Cl)FePc for the
ORR. Of all self-assembled catalysts tested, the highest catalytic
activity was exhibited by the Au(111)/Up/FePc system. XPS measurements
and DFT calculations showed that it is possible to tailor the FePc–N(pyridiniums)
Fe–O2 binding energies, by changing the core positions
and affecting the “pull effect” of pyridiniums. This
affects directly the catalytic activity of FePcs. The plot of activity
as (log I)E versus the calculated Fe–O2 binding energies gives an activity volcano correlation, indicating
that an optimum binding energy of O2 with the Fe center
provides the highest activity.
A conformationally flexible calix [4]pyrrole possessing a conjugated electronic structure (an N-substituted oxoporphyrinogen (OxP) related to porphyrin) was used to investigate the influence of mechanical stretching on the single-molecule conductance of these molecules using the mechanicallycontrolled break junction (MCBJ) technique. The results show that the molecule can be immobilized in a single-molecule break junction configuration, giving rise to different behaviours.These include step-like features in the conductance vs. displacement traces as well as conductance traces that exhibit a slower decay ('downhill' traces) than measured for direct tunneling. The latter class of traces can be associated with the mechanical manipulation (i. e., stretching) of the molecule with inter-electrode distances as long as 2 nm. Density functional theory (DFT) calculations reveal that OxP molecules are stable under stretching in the length regime studied.
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