Iron-based trinuclear metal-organic nanostructures on a surface with local charge accumulation

Cornelius Krull, Marina Castelli, Prokop Hapala, Dhaneesh Kumar, Pavel Jelinek and Agustin Schiffrin

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Received: 8th February 18

Coordination chemistry relies on harnessing active metal sites within organic matrices. Polynuclear complexes – consisting of organic ligands binding to clusters of several metal atoms – are of particular interest, owing to their electronic/magnetic properties and potential for functional reactivity pathways. However, their synthesis remains challenging; only a limited number of geometries and configurations have been achieved. Here, we synthesise – via supramolecular chemistry on a noble metal surface – one-dimensional metal-organic nanostructures composed of terpyridine (tpy)-based molecules coordinated with well-defined polynuclear iron clusters. By a combination of low-temperature scanning probe microscopy techniques and density functional theory, we demonstrate that the coordination motif consists of coplanar tpy’s linked via a linear tri-iron node in a mixed (positive) valence, metal-metal bond configuration. This unusual linkage is stabilized by a local accumulation of electrons at the interface between cations, ligand and surface. The latter, enabled by the bottom-up on-surface synthesis, hints at a chemically active metal centre, and opens the door to the engineering of nanomaterials with novel catalytic and magnetic functionalities.

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