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

Research output: Contribution to journalArticleResearchpeer-review

Abstract

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
Volume9
Issue number1
DOIs
Publication statusPublished - 1 Dec 2018

Cite this

Krull, Cornelius ; Castelli, Marina ; Hapala, Prokop ; Kumar, Dhaneesh ; Tadich, Anton ; Capsoni, Martina ; Edmonds, Mark T. ; Hellerstedt, Jack ; Burke, Sarah A. ; Jelinek, Pavel ; Schiffrin, Agustin. / Iron-based trinuclear metal-organic nanostructures on a surface with local charge accumulation. In: Nature Communications. 2018 ; Vol. 9, No. 1.
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abstract = "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.",
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Iron-based trinuclear metal-organic nanostructures on a surface with local charge accumulation. / Krull, Cornelius; Castelli, Marina; Hapala, Prokop; Kumar, Dhaneesh; Tadich, Anton; Capsoni, Martina; Edmonds, Mark T.; Hellerstedt, Jack; Burke, Sarah A.; Jelinek, Pavel; Schiffrin, Agustin.

In: Nature Communications, Vol. 9, No. 1, 3211, 01.12.2018.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Castelli, Marina

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AU - Capsoni, Martina

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