Redox-Active On-Surface Assembly of Metal–Organic Chains with Single-Site Pt(II)

The formation and stabilization of well-defined transition-metal single sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts. Organic ligand coordination to produce a well-defined oxidation state in weakly reducing metal sites at surfaces, desirable for selective catalysis, has not been achieved. Here, we address this using metallic platinum interacting with a dipyridyl tetrazine ligand on a single crystal gold surface. X-ray photoelectron spectroscopy measurements demonstrate the metal-ligand redox activity and are paired with molecular-resolution scanning probe microscopy to elucidate the structure of the metal-organic network. Comparison to the redox-inactive diphenyl tetrazine ligand as a control experiment illustrates that the redox activity and molecular-level ordering at the surface rely on two key elements of the metal complexes: (i) bidentate binding sites providing a suitable square-planar coordination geometry when paired around each Pt, and (ii) redox-active functional groups to enable charge transfer to a well-defined Pt(II) oxidation state. Ligand-mediated control over the oxidation state and structure of single-site metal centers that are in contact with a metal surface may enable advances in higher selectivity for next generation heterogeneous catalysts.