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The synthesis of electrode-attached Rh(I) diisocyanide coordination polymers that incorporate a series of arylene diisocyanide linkers and which are grown from gold surfaces by a bottom-up, layer-by-layer procedure that allows for a high level of control for the film thickness is reported. A seed layer of the arylene diisocyanide ligand is used to template directional growth of the coordination polymer made using the well-studied square-planar rhodium tetrakis(isocyanide) as the metal node. Materials ranging from 1 to 30 layers were prepared via layer-by-layer solution-phase deposition. Characterization of the polymer films using scanning electron microscopy and ellipsometry shows layer-by-layer control in these films with linear thickness growth per layer. Phasemodulated infrared reflection absorption spectroscopy (PM-IRRAS), diffuse reflectance UV−vis, and X-ray photoelectron spectroscopy (XPS) were used to confirm the structures of the films. Although prior reports of related coordination polymers and films based on diisocyanides showed considerable air-instability, the films reported here demonstrate significantly improved chemical stability and electrochemical stability at a moderately high applied bias. Electrochemical characterization and ex situ XPS demonstrate that these diisocyanide films are stable to stripping at potentials up to −2.2 V versus decamethylferrocene in acetonitrile, supporting their relevance for electrochemical applications. 

The synthesis, structure, and reactivity of a μ₃-SnH capped trinuclear nickel cluster, [Ni₃(dppm)₃(μ₃-H)(μ₃-SnH)], is reported. This complex undergoes oxidative addition chemistry, alkyne insertion, and subsequent hydrogenation.