Sun, Qiang; Mateo, Luis M; Robles, Roberto; Ruffieux, Pascal; Bottari, Giovanni; Torres, Tomás; Fasel, Roman; Lorente, Nicolás (2022). Magnetic Interplay between π-Electrons of Open-Shell Porphyrins and d-Electrons of Their Central Transition Metal Ions. Advanced science, 9(19), e2105906. Wiley 10.1002/advs.202105906
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Magnetic_Interplay_between__Electrons_of_Open_Shell_Porphyrins_and_d_Electrons_of_Their.pdf - Published Version Available under License Creative Commons: Attribution (CC-BY). Download (3MB) | Preview |
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 dz 2 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.
Item Type: |
Journal Article (Original Article) |
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Division/Institute: |
08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP) |
UniBE Contributor: |
Fasel, Roman |
Subjects: |
500 Science > 570 Life sciences; biology 500 Science > 540 Chemistry |
ISSN: |
2198-3844 |
Publisher: |
Wiley |
Language: |
English |
Submitter: |
Pubmed Import |
Date Deposited: |
21 Mar 2022 14:53 |
Last Modified: |
05 Dec 2022 16:15 |
Publisher DOI: |
10.1002/advs.202105906 |
PubMed ID: |
35302718 |
Uncontrolled Keywords: |
density functional theory calculations molecular magnetism on-surface synthesis organic open-shell compounds porphyrins |
BORIS DOI: |
10.48350/167643 |
URI: |
https://boris.unibe.ch/id/eprint/167643 |
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