The formation of metal-organic complexes on metal surfaces is a research topic of high interest to develop tunable functional surfaces, including advances in catalysis. One such focus of this research is the formation of single site metal centers that have uniform ligand environments and thus uniform chemistry. We report the formation of metal complexes with the ligand di-pyridyltetrazine (DPTZ) on the Ag(111) surface and the reconstructed Au(100) surface. Each metal center binds to two DPTZ molecules resulting in 1D supramolecular chains of quasi-square-planar metal coordination across the surface. Pt complexation occurs immediately after Pt deposition at room temperature on either surface. This complexation is improved with annealing the co-adsorbed species to 170 °C on Au(100). In the absence of Pt co-deposition, complexation of DPTZ with atoms from the substrate on Ag(111) starts to be observed when annealing to 110 °C, yielding Ag-DPTZ. No similar complexation with substrate atoms is seen on Au(100). The complexation of DPTZ with substrate atoms on Ag(111) takes place even when the DPTZ is already complexed to Pt, <i>i.e.</i>, Ag adatoms from Ag(111) will replace Pt when it is coordinated to DPTZ. The complexation of DTPZ to Ag occurs at 80 °C if the DPTZ is first complexed to Pt, but requires annealing to 110 °C without Pt. The metal-organic complexes are characterized by high-resolution electron energy loss spectroscopy (HREELS), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS). This research is among the few to use HREELS to characterize the formation of extended metal organic networks on a surface formed though the redox of the organic species into an anionic state.

Metal-ligand complexation through redox assembly at surfaces characterized by vibrational spectroscopy

254th National Meeting (2017)

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