Cornelius Krull1, Marina Castelli1,2, Prokop Hapala3, Dhaneesh Kumar1,2,4, Anton Tadich5, Martina Capsoni6, Mark T Edmonds1,2,4, Jack Hellerstedt1,2,3, Sarah A Burke6,7,8, Pavel Jelinek9,10, Agustin Schiffrin11,12,13. 1. School of Physics & Astronomy, Monash University, 19 Rainforest Walk, Clayton, 3800, Australia. 2. Monash Centre for Atomically Thin Materials, Monash University, 20 Research Way, Clayton, 3800, Australia. 3. Institute of Physics of the CAS, Cukrovarnicka 10, Prague, 16200, Czech Republic. 4. ARC Centre of Excellence in Future Low-Energy Electronics Technologies, Monash University, 19 Rainforest Walk, Clayton, 3800, Australia. 5. Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria, 3168, Australia. 6. Department of Physics and Astronomy, University of British Columbia, 6224 Agricultural Road, Vancouver, British Columbia, Canada, V6T 1Z1. 7. Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, Canada, V6T 1Z1. 8. Stewart Blusson Quantum Matter Institute, University of British Columbia, 2355 East Mall, Vancouver, British Columbia, Canada, V6T 1Z4. 9. Institute of Physics of the CAS, Cukrovarnicka 10, Prague, 16200, Czech Republic. jelinekp@fzu.cz. 10. RCPTM, Palacky University, Šlechtitelů 27, 783 71, Olomouc, Czech Republic. jelinekp@fzu.cz. 11. School of Physics & Astronomy, Monash University, 19 Rainforest Walk, Clayton, 3800, Australia. agustin.schiffrin@monash.edu. 12. Monash Centre for Atomically Thin Materials, Monash University, 20 Research Way, Clayton, 3800, Australia. agustin.schiffrin@monash.edu. 13. ARC Centre of Excellence in Future Low-Energy Electronics Technologies, Monash University, 19 Rainforest Walk, Clayton, 3800, Australia. agustin.schiffrin@monash.edu.
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 tpy's 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.
Coordination chemistry relies on harnessing active n class="Chemical">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 tpy's 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.
Authors: Chao Jing; Bodong Zhang; Sabine Synkule; Maryam Ebrahimi; Alexander Riss; Willi Auwärter; Li Jiang; Guillaume Médard; Joachim Reichert; Johannes V Barth; Anthoula C Papageorgiou Journal: Angew Chem Int Ed Engl Date: 2019-11-27 Impact factor: 15.336