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

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


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.Comment: 7 pages, 4 figures, 14 pages supporting informatio

Topics: Condensed Matter - Mesoscale and Nanoscale Physics, Condensed Matter - Materials Science, Physics - Chemical Physics
Publisher: 'Springer Science and Business Media LLC'
Year: 2018
DOI identifier: 10.1038/s41467-018-05543-4
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