Coordinative Self‐assembly of π‐Electron Magnetic Porphyrins
π-Electron magnetic compounds on surfaces have emerged as a powerful platform to interrogate spin interactions at the atomic scale, with great potential in spintronics and quantum technologies. A key challenge is organizing these compounds over large length scales, while elucidating their resulting magnetic properties. Herein, we offer a relevant contribution toward this objective, which consists of using on-surface synthesis coupled with coordination chemistry to promote the self-assembly of π-electron magnetic porphyrin species. A porphyrin precursor equipped with carbonitrile moieties in a trans arrangement was prepared by solution synthesis and deposited on Au(111)/mica. Depending on the specific growth protocol, surface-promoted reactions led to the transformation of the precursor into non-magnetic Au-CN coordinated porphyrin monomers, covalent porphyrin dimers, and one-dimensional porphyrin polymers (based on porphyrin monomers or covalent porphyrin dimers), as revealed by scanning probe microscopy studies combined with theoretical calculations. Interestingly, the scanning tunneling microscopy tip could convert such closed-shell porphyrin units into open-shell species by the removal of some peripheral hydrogen atoms. The magnetic features (i.e., singlet or triplet ground state) of the porphyrin units comprising the polymers were investigated for polymers of different lengths. No magnetic exchange coupling between adjacent units was observed, suggesting protection of the magnetic entities.
Authors
- Koen Lauwaet (ORCID: https://orcid.org/0000-0003-1024-6779)
- José Ignacio Urgel (ORCID: https://orcid.org/0000-0001-7608-2979)
- Rodolfo Miranda (ORCID: https://orcid.org/0000-0002-1064-6724)
- Kalyan Biswas (ORCID: https://orcid.org/0000-0002-1951-5595)
- Tomás Torres⊗ (ORCID: https://orcid.org/0000-0001-9335-6935)
- Diego Soler‐Polo (ORCID: https://orcid.org/0000-0001-9215-4151)
- Pavel Jelı́nek (ORCID: https://orcid.org/0000-0002-5645-8542)
- Maxence Urbani (ORCID: https://orcid.org/0000-0001-7733-6440)
- Shanmugasibi K. Mathialagan (ORCID: https://orcid.org/0000-0003-2910-7429)
- Sofía O. Parreiras (ORCID: https://orcid.org/0000-0001-9009-1994)
- Lenka Černá (ORCID: https://orcid.org/0009-0004-5469-5028)
- David Écija (ORCID: https://orcid.org/0000-0002-8661-8295)
- Giovanni Bottari (ORCID: https://orcid.org/0000-0001-8392-2649)
- José M. Gallego (ORCID: https://orcid.org/0000-0003-1716-0126)
- Miguel Martínez García (ORCID: https://orcid.org/0009-0002-3353-874X)
- María Tenorio (ORCID: https://orcid.org/0000-0002-0632-1636)
- Marco Lozano
Institutions
- Madrid Institute for Advanced Studies (ES)
- Consejo Superior de Investigaciones Científicas (ES)
- Czech Academy of Sciences (CZ)
- IMDEA Nanoscience (ES)
- Instituto de Ciencia de Materiales de Madrid (ES)
- Regional Centre of Advanced Technologies and Materials (CZ)
- FZU ‒ Institute of Physics of the Academy of Sciences of the Czech Republic (CZ)
- Akademie (Czechia) (CZ)
- Universidad Autónoma de Madrid (ES)
- Palacký University Olomouc (CZ)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2024-12-06
- DOI
- https://doi.org/10.1002/anie.202420572
- Citations
- 8
- Primary Topic
- Surface Chemistry and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 1.48
Funders
- Alexander von Humboldt-Stiftung
- Comunidad de Madrid
- European Commission
- Ministerstvo Školství, Mládeže a Tělovýchovy
- Grantová Agentura České Republiky
- Agencia Estatal de Investigación