Single atom coordination in a manganese–cobalt bi-metallic framework on graphene: geometric and electronic structures
Manganese tetra-pyridyl-porphyrins are found to self-organize in an ordered monolayer on graphene. Moreover, post deposition of cobalt ad-atoms steers the geometric reordering of the layer, yielding the formation of a self-assembled bimetallic network, where both Mn and Co are tetra-coordinated with nitrogen. While manganese shifts from Mn(II) towards the +2/+3 oxidation state range, depending on the local Co concentration and not reaching a full Mn(III) configuration, pyridinic cobalt is stabilized in the rarer +1 oxidation state. The actual geometric and electronic structures of the framework are defined by lateral interactions, dominating over the weaker network-graphene bonding.
Authors
- Pierluigi Gargiani (ORCID: https://orcid.org/0000-0002-6649-0538)
- Paolo Giannozzi (ORCID: https://orcid.org/0000-0002-9635-3227)
- Nikolay A. Vinogradov (ORCID: https://orcid.org/0000-0002-1477-853X)
- Basant Roondhe (ORCID: https://orcid.org/0000-0003-0396-8829)
- Mattia Scardamaglia (ORCID: https://orcid.org/0000-0002-1128-7524)
- Davide Bidoggia (ORCID: https://orcid.org/0000-0002-0757-1397)
- Giovanni Zamborlini (ORCID: https://orcid.org/0000-0002-0460-4958)
- Valentin Mischke
- Mirko Cinchetti (ORCID: https://orcid.org/0000-0003-0735-8921)
- Manuel Valvidares (ORCID: https://orcid.org/0000-0003-4895-8114)
- Asha Yadav (ORCID: https://orcid.org/0000-0001-7967-9279)
- Erik Vesselli (ORCID: https://orcid.org/0000-0002-6799-0032)
- Stefania Baronio
- Alessandro Namar (ORCID: https://orcid.org/0009-0009-1963-7283)
- Michela De Col (ORCID: https://orcid.org/0000-0002-9486-3506)
- Olga Resel
Institutions
- University of Udine (IT)
- University of Trieste (IT)
- University of Graz (AT)
- Lund University (SE)
- TU Dortmund University (DE)
- AREA Science Park (IT)
- ALBA Synchrotron (Spain) (ES)
- Istituto Officina dei Materiali (IT)
- Nawi Graz (AT)
- MAX IV Laboratory (SE)
Publication Details
- Journal
- Nanoscale
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5nr01383f
- Citations
- 1
- Primary Topic
- Porphyrin and Phthalocyanine Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.52
Funders
- Deutsche Forschungsgemeinschaft
- VINNOVA
- Svenska Forskningsrådet Formas
- Vetenskapsrådet
- Ministerium für Kultur und Wissenschaft des Landes Nordrhein-Westfalen
- Horizon 2020 Framework Programme