Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
Magnetism is typically associated with d- or f-block elements, but can also appear in organic molecules with unpaired π-electrons. This has considerably boosted the interest in such organic materials with large potential for spintronics and quantum applications. While several materials showing eithe...
| Authors: | ; ; ; ; ; ; ; |
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| Format: | Article |
| Publication date: | 2022 |
| Country: | España |
| Institution: | Universidad Autónoma de Madrid |
| Repository: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Language: | English |
| OAI Identifier: | oai:repositorio.uam.es:10486/706355 |
| Online Access: | http://hdl.handle.net/10486/706355 https://dx.doi.org/10.1002/advs.202105906 |
| Access Level: | Open access |
| Keyword: | Electrons Iron Compounds Magnetism Metal Ions Shells (Structures) Transition Metals Química |
| _version_ | 1878735048704786432 |
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| author | Sun, Qiang |
| author2 | Mateo De Doni, Luis Manuel Robles, Roberto Ruffieux, Pascal Bottari, Giovanni Torres Cebada, Tomás Fasel, Roman Lorente, Nicolás |
| author2_role | author author author author author author author |
| author_browse | Bottari, Giovanni Fasel, Roman Lorente, Nicolás Mateo De Doni, Luis Manuel Robles, Roberto Ruffieux, Pascal Sun, Qiang Torres Cebada, Tomás |
| author_facet | Sun, Qiang Mateo De Doni, Luis Manuel Robles, Roberto Ruffieux, Pascal Bottari, Giovanni Torres Cebada, Tomás Fasel, Roman Lorente, Nicolás |
| author_role | author |
| collection | Biblos-e Archivo. Repositorio Institucional de la UAM |
| description | Magnetism is typically associated with d- or f-block elements, but can also appear in organic molecules with unpaired π-electrons. This has considerably boosted the interest in such organic materials with large potential for spintronics and quantum applications. While several materials showing either d/f or π-electron magnetism have been synthesized, the combination of both features within the same structure has only scarcely been reported. Open-shell porphyrins (Pors) incorporating d-block transition metal ions represent an ideal platform for the realization of such architectures. Herein, the preparation of a series of open-shell, π-extended Pors that contain magnetically active metal ions (i.e., CuII, CoII, and FeII) through a combination of in-solution and on-surface synthesis is reported. A detailed study of the magnetic interplay between π- and d-electrons in these metalloPors has been performed by scanning probe methods and density functional theory calculations. For the Cu and FePors, ferromagnetically coupled π-electrons are determined to be delocalized over the Por edges. For the CoPor, the authors find a Kondo resonance resulting from the singly occupied CoII dz2 orbital to dominate the magnetic fingerprint. The Fe derivative exhibits the highest magnetization of 3.67 μB (S≈2) and an exchange coupling of 16 meV between the π-electrons and the Fe d-states |
| eu_rights_str_mv | openAccess |
| format | article |
| id | ES_74ee82bf4d72efccdd895ddfe5a2cdbe |
| institution | Universidad Autónoma de Madrid |
| instname_str | Universidad Autónoma de Madrid |
| language | eng |
| network_acronym_str | ES |
| network_name_str | España |
| oai_identifier_str | oai:repositorio.uam.es:10486/706355 |
| publishDate | 2022 |
| publishDateSort | 2022 |
| publisher | Wiley Open Access |
| publisherStr | Wiley Open Access |
| reponame_str | Biblos-e Archivo. Repositorio Institucional de la UAM |
| spelling | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions Sun, Qiang Mateo De Doni, Luis Manuel Robles, Roberto Ruffieux, Pascal Bottari, Giovanni Torres Cebada, Tomás Fasel, Roman Lorente, Nicolás Electrons Iron Compounds Magnetism Metal Ions Shells (Structures) Transition Metals Química Magnetism is typically associated with d- or f-block elements, but can also appear in organic molecules with unpaired π-electrons. This has considerably boosted the interest in such organic materials with large potential for spintronics and quantum applications. While several materials showing either d/f or π-electron magnetism have been synthesized, the combination of both features within the same structure has only scarcely been reported. Open-shell porphyrins (Pors) incorporating d-block transition metal ions represent an ideal platform for the realization of such architectures. Herein, the preparation of a series of open-shell, π-extended Pors that contain magnetically active metal ions (i.e., CuII, CoII, and FeII) through a combination of in-solution and on-surface synthesis is reported. A detailed study of the magnetic interplay between π- and d-electrons in these metalloPors has been performed by scanning probe methods and density functional theory calculations. For the Cu and FePors, ferromagnetically coupled π-electrons are determined to be delocalized over the Por edges. For the CoPor, the authors find a Kondo resonance resulting from the singly occupied CoII dz2 orbital to dominate the magnetic fingerprint. The Fe derivative exhibits the highest magnetization of 3.67 μB (S≈2) and an exchange coupling of 16 meV between the π-electrons and the Fe d-states Wiley Open Access http://hdl.handle.net/10486/706355 https://dx.doi.org/10.1002/advs.202105906 |
| spellingShingle | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions Sun, Qiang Electrons Iron Compounds Magnetism Metal Ions Shells (Structures) Transition Metals Química |
| title | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions |
| title_full | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions |
| title_fullStr | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions |
| title_full_unstemmed | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions |
| title_short | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions |
| title_sort | Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions |
| topic | Electrons Iron Compounds Magnetism Metal Ions Shells (Structures) Transition Metals Química |
| topic_facet | Electrons Iron Compounds Magnetism Metal Ions Shells (Structures) Transition Metals Química |
| url | http://hdl.handle.net/10486/706355 https://dx.doi.org/10.1002/advs.202105906 |