Harnessing π-d magnetic interactions in Co porphyrins by metal-ligand coordination
7 affiliations
- 1Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanoscience
- 2IMDEA Nanoscience
- 3Unidad asociada al CSIC por el ICMM
- 4Departamento de Química Orgánica
- 5Universidad Autónoma de Madrid
- 6Institute for Advanced Research in Chemical Sciences
- 7Universidad Autónoma de Madrid
Abstract
π-Multiradicalic compounds fabricated by on-surface synthesis have emerged as a powerful platform to interrogate spin interactions at the atomic scale. However, the introduction and role of unpaired d-electrons on such systems, and the study of π-d electronic interactions, are still incipient. In this context, a crucial point is the tunability of the inherent magnetic properties of such π-d architectures by incorporation of peripheral metal-organic coordination, which at the same time allows creating self-assembled architectures. Herein, to this aim we exploit an ex-professo synthesized Zn-porphyrin (1) equipped with two carbonitrile-dimethyl-phenyl moieties at its trans-meso positions, which forms π-extended metallo-organic nanostructures featuring unpaired π-electrons through cyclodehydrogenation and concomitant carbonitrile-gold coordination. Transmetallation of such Zn-based nanoarchitectures with Co atoms gave rise to the several Co-based porphyrin multiradicalic species featuring both unpaired π and d electrons, including porphyrin monomers (CoPor M) and dimers (Co-Por D) as well as one-dimensional porphyrin nanochains (1D CoPor NC) and nanotapes (1D CoPor NT). Scanning probe spectroscopy combined with theoretical calculations reveal that the carbonitrile-gold coordination environment dramatically alters the magnetic structure of the cobalt center as compared to analogue porphyrin species lacking the CN group. On the one hand, in both CoPor M and 1D CoPor NC the cobalt atom presents a S=3/2 ground state versus the S=1/2 case for Co porphyrins analogues lacking the nitrile moiety. Additionally, no Kondo interactions are detected at the metal center, as a consequence of a diminished magnetic interaction of CoPor M and 1D CoPor NC with the Au(111) substrate. On the other hand, CoPor D presents two radical electrons distributed between the cobalt atoms and the carbon π-system which interact ferromagnetically yielding a S=1 ground state. Our findings demonstrate how metal-ligand coordination can be used to harness the magnetic interactions within surface-supported multiradicalic molecular systems.
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BibTeX
@misc{tenorio2026harnessing,
title = {{Harnessing π-d magnetic interactions in Co porphyrins by metal-ligand coordination}},
author = {María Tenorio and Lenka Cerna and Marco Lozano and Ana Barragán and Miguel Martínez García and Aurelio Gallardo and Koen Lauwaet and Shanmugasibi K. Mathialagan and Sofía O. Parreiras and José M. Gallego and José Ignacio Urgel and Tomás Torres and Diego Soler-Polo and Giovanni Bottari and David Écija},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009863/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009863/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Harnessing π-d magnetic interactions in Co porphyrins by metal-ligand coordination
AU - María Tenorio
AU - Lenka Cerna
AU - Marco Lozano
AU - Ana Barragán
AU - Miguel Martínez García
AU - Aurelio Gallardo
AU - Koen Lauwaet
AU - Shanmugasibi K. Mathialagan
AU - Sofía O. Parreiras
AU - José M. Gallego
AU - José Ignacio Urgel
AU - Tomás Torres
AU - Diego Soler-Polo
AU - Giovanni Bottari
AU - David Écija
PY - 2026
DA - 2026/10/05
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009863/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009863/v1
AB - π-Multiradicalic compounds fabricated by on-surface synthesis have emerged as a powerful platform to interrogate spin interactions at the atomic scale. However, the introduction and role of unpaired d-electrons on such systems, and the study of π-d electronic interactions, are still incipient. In this context, a crucial point is the tunability of the inherent magnetic properties of such π-d architectures by incorporation of peripheral metal-organic coordination, which at the same time allows creating self-assembled architectures. Herein, to this aim we exploit an ex-professo synthesized Zn-porphyrin (1) equipped with two carbonitrile-dimethyl-phenyl moieties at its trans-meso positions, which forms π-extended metallo-organic nanostructures featuring unpaired π-electrons through cyclodehydrogenation and concomitant carbonitrile-gold coordination. Transmetallation of such Zn-based nanoarchitectures with Co atoms gave rise to the several Co-based porphyrin multiradicalic species featuring both unpaired π and d electrons, including porphyrin monomers (CoPor M) and dimers (Co-Por D) as well as one-dimensional porphyrin nanochains (1D CoPor NC) and nanotapes (1D CoPor NT). Scanning probe spectroscopy combined with theoretical calculations reveal that the carbonitrile-gold coordination environment dramatically alters the magnetic structure of the cobalt center as compared to analogue porphyrin species lacking the CN group. On the one hand, in both CoPor M and 1D CoPor NC the cobalt atom presents a S=3/2 ground state versus the S=1/2 case for Co porphyrins analogues lacking the nitrile moiety. Additionally, no Kondo interactions are detected at the metal center, as a consequence of a diminished magnetic interaction of CoPor M and 1D CoPor NC with the Au(111) substrate. On the other hand, CoPor D presents two radical electrons distributed between the cobalt atoms and the carbon π-system which interact ferromagnetically yielding a S=1 ground state. Our findings demonstrate how metal-ligand coordination can be used to harness the magnetic interactions within surface-supported multiradicalic molecular systems.
ER -