The development of highly ordered, conductive, porous materials bound to an electrode surface is desirable for application to problems in molecular electronics, sensors, and catalysis. We are investigating electrode-attached, conductive Rh(I) diisocyanide coordination polymers grown from gold surfaces in a bottom-up procedure. We use a seed layer of an aryl diisocyanide on the gold electrode to template growth of the coordination polymer with Rh(I) centers joining a variety of possible diisocyanide linkers in a square planar geometry. The coordination polymer is prepared via layer-by-layer solution-phase deposition. The structure is comprised of 2-D sheets perpendicular to the gold surface, while Rh-Rh bonding between sheets occurs, improving the conductivity. Prior work with this coordination polymer has only reported preparation of a powder whose conductivity is affected by grain boundaries and disorder. Characterization of our ordered film by IR, XPS, ellipsometry, SEM, UV-vis, and XRD indicates layer-by-layer control and Rh-Rh interaction. Characterization of conductivity by JV-curve analysis and of electrochemical stability by voltammetry explores relevance to electrochemical applications. Our ongoing efforts involve integration of electrochemical catalysts for CO<sub>2</sub> reduction in the structure, which could improve upon the present state of the art in molecular catalysis by providing approaches to stabilizing catalysts against degradation, improving recyclability, and making separation of products more facile.

Bottom-up preparation of ordered Rh(I) diisocyanide coordination polymers on gold surfaces and their conductivity and electrochemical stability

253rd National Meeting (2017)

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