2 research outputs found
Iridium(III) Bis-Pyridine-2-Sulfonamide Complexes as Efficient and Durable Catalysts for Homogeneous Water Oxidation
A family of tetradentate bisÂ(pyridine-2-sulfonamide)
(bpsa) compounds was synthesized as a ligand platform for designing
resilient and electronically tunable catalysts capable of performing
water oxidation catalysis and other processes in highly oxidizing
environments. These wrap-around ligands were coordinated to IrÂ(III)
octahedrally, forming an anionic complex with chloride ions bound
to the two remaining coordination sites. NMR spectroscopy documented
that the more rigid ligand frameworksî—¸[IrÂ(bpsa-Cy)ÂCl<sub>2</sub>]<sup>−</sup> and [IrÂ(bpsa-Ph)ÂCl<sub>2</sub>]<sup>−</sup>î—¸produced <i>C</i><sub>1</sub>-symmetric complexes,
while the complex with the more flexible ethylene linker in [IrÂ(bpsa-en)ÂCl<sub>2</sub>]<sup>−</sup> displays <i>C</i><sub>2</sub> symmetry. Their electronic structure was explored with DFT calculations
and cyclic voltammetry in nonaqueous environments, which unveiled
highly reversible IrÂ(III)/IrÂ(IV) redox processes and more complex,
irreversible reduction chemistry. Addition of water to the electrolyte
revealed the ability of these complexes to catalyze the water oxidation
reaction efficiently. Electrochemical quartz crystal microbalance
studies confirmed that a molecular species is responsible for the
observed electrocatalytic behavior and ruled out the formation of
active IrO<sub><i>x</i></sub>. The electrochemical studies
were complemented by work on chemically driven water oxidation, where
the catalytic activity of the iridium complexes was studied upon exposure
to ceric ammonium nitrate, a strong, one-electron oxidant. Variation
of the catalyst concentrations helped to illuminate the kinetics of
these water oxidation processes and highlighted the robustness of
these systems. Stable performance for over 10 days with thousands
of catalyst turnovers was observed with the <i>C</i><sub>1</sub>-symmetric catalysts. Dynamic light scattering experiments
ascertained that a molecular species is responsible for the catalytic
activity and excluded the formation of IrO<sub><i>x</i></sub> particles
Toward Quantifying the Electrostatic Transduction Mechanism in Carbon Nanotube Molecular Sensors
Despite the great promise of carbon nanotube field-effect
transistors
(CNT FETs) for applications in chemical and biochemical detection,
a quantitative understanding of sensor responses is lacking. To explore
the role of electrostatics in sensor transduction, experiments were
conducted with a set of highly similar compounds designed to adsorb
onto the CNT FET via a pyrene linker group and take on a set of known
charge states under ambient conditions. Acidic and basic species were
observed to induce threshold voltage shifts of opposite sign, consistent
with gating of the CNT FET by local charges due to protonation or
deprotonation of the pyrene compounds by interfacial water. The magnitude
of the gate voltage shift was controlled by the distance between the
charged group and the CNT. Additionally, functionalization with an
uncharged pyrene compound showed a threshold shift ascribed to its
molecular dipole moment. This work illustrates a method for producing
CNT FETs with controlled values of the turnoff gate voltage, and more
generally, these results will inform the development of quantitative
models for the response of CNT FET chemical and biochemical sensors