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

Cornelius Krull, Marina Castelli, Prokop Hapala, Dhaneesh Kumar, Anton Tadich, Martina Capsoni, Mark T. Edmonds, Jack Hellerstedt, Sarah A. Burke, Pavel Jelinek, Agustin Schiffrin

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Coordination chemistry relies on harnessing active metal sites within organic matrices. Polynuclear complexes—where organic ligands bind to several metal atoms—are relevant due to their electronic/magnetic properties and potential for functional reactivity pathways. However, their synthesis remains challenging; few 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. Combining low-temperature scanning probe microscopy and density functional theory, we demonstrate that the coordination motif consists of coplanar tpyʼs linked via a quasi-linear tri-iron node in a mixed (positive-)valence metal–metal bond configuration. This unusual linkage is stabilised by local accumulation of electrons between cations, ligand and surface. The latter, enabled by bottom-up on-surface synthesis, yields an electronic structure that hints at a chemically active polynuclear metal centre, paving the way for nanomaterials with novel catalytic/magnetic functionalities.

Original languageEnglish
Article number3211
Number of pages7
JournalNature Communications
Issue number1
Publication statusPublished - 1 Dec 2018

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