Designing optoelectronic properties by on-surface synthesis: formation and electronic structure of an iron-terpyridine macromolecular complex
Supramolecular chemistry protocols applied on surfaces offer compelling avenues for atomic scale control over organic-inorganic interface structures. In this approach, adsorbate-surface interactions and two-dimensional confinement can lead to morphologies and properties that differ dramatically from those achieved via conventional synthetic approaches. Here, we describe the bottom-up, on-surface synthesis of one-dimensional coordination nanostructures based on an iron (Fe)-terpyridine (tpy) interaction borrowed from functional metal-organic complexes used in photovoltaic and catalytic applications. Thermally activated diffusion of sequentially deposited ligands and metal atoms, and intra-ligand conformational changes, lead to Fe-tpy coordination and formation of these nanochains. Low-temperature Scanning Tunneling Microscopy and Density Functional Theory were used to elucidate the atomic-scale morphology of the system, providing evidence of a linear tri-Fe linkage between facing, coplanar tpy groups. Scanning Tunneling Spectroscopy reveals highest occupied orbitals with dominant contributions from states located at the Fe node, and ligand states that mostly contribute to the lowest unoccupied orbitals. This electronic structure yields potential for hosting photo-induced metal-to-ligand charge transfer in the visible/near-infrared. The formation of this unusual tpy/tri-Fe/tpy coordination motif has not been observed for wet chemistry synthesis methods, and is mediated by the bottom-up on-surface approach used here.