Oxygen-Donor Metalloligands Induce Slow Magnetization Relaxation in Zero Field for a Cobalt(II) Complex with {CoO4} Motif
Most 3d metal-based single-molecule magnets (SMMs) use N-ligands or ligands with even softer donors to impart a particular coordination geometry and increase the zero-field splitting parameter |D|, while complexes with hard O-donor ligands showing slow magnetization relaxation are rare. Here, we report that a diamagnetic NiII complex of a tetradentate ligand featuring two N-heterocyclic carbene and two alkoxide-O donors, [LO,ONi], can serve as a {O,O'}-chelating metalloligand to give a trinuclear complex [(LO,ONi)Co(LO,ONi)](OTf)2 (2) with an elongated tetrahedral {CoIIO4} core, D = -74.3 cm-1, and a spin reversal barrier Ueff = 86.9 cm-1 in the absence of an external dc field. The influence of diamagnetic NiII on the electronic structure of the {CoO4} unit in comparison to [Co(OPh)4]2- (A) has been probed with multireference ab initio calculations. These reveal a contrapolarizing effect of the NiII, which forms stronger metal-alkoxide bonds than the central CoII, inducing a change in ligand field splitting and a 5-fold increase in the magnetic anisotropy in 2 compared to A, with an easy magnetization axis along the Ni-Co-Ni vector. This demonstrates a strategy to enhance the SMM properties of 3d metal complexes with hard O-donors by modulating the ligand field character via the coordination of diamagnetic ions and the benefit of robust metalloligands in that regard.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:63 |
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| Enthalten in: |
Inorganic chemistry - 63(2024), 12 vom: 25. März, Seite 5652-5663 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Lococciolo, Giuseppe [VerfasserIn] |
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| Anmerkungen: |
Date Revised 29.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.inorgchem.4c00054 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM369600592 |
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| 100 | 1 | |a Lococciolo, Giuseppe |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Oxygen-Donor Metalloligands Induce Slow Magnetization Relaxation in Zero Field for a Cobalt(II) Complex with {CoO4} Motif |
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| 500 | |a Date Revised 29.03.2024 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Most 3d metal-based single-molecule magnets (SMMs) use N-ligands or ligands with even softer donors to impart a particular coordination geometry and increase the zero-field splitting parameter |D|, while complexes with hard O-donor ligands showing slow magnetization relaxation are rare. Here, we report that a diamagnetic NiII complex of a tetradentate ligand featuring two N-heterocyclic carbene and two alkoxide-O donors, [LO,ONi], can serve as a {O,O'}-chelating metalloligand to give a trinuclear complex [(LO,ONi)Co(LO,ONi)](OTf)2 (2) with an elongated tetrahedral {CoIIO4} core, D = -74.3 cm-1, and a spin reversal barrier Ueff = 86.9 cm-1 in the absence of an external dc field. The influence of diamagnetic NiII on the electronic structure of the {CoO4} unit in comparison to [Co(OPh)4]2- (A) has been probed with multireference ab initio calculations. These reveal a contrapolarizing effect of the NiII, which forms stronger metal-alkoxide bonds than the central CoII, inducing a change in ligand field splitting and a 5-fold increase in the magnetic anisotropy in 2 compared to A, with an easy magnetization axis along the Ni-Co-Ni vector. This demonstrates a strategy to enhance the SMM properties of 3d metal complexes with hard O-donors by modulating the ligand field character via the coordination of diamagnetic ions and the benefit of robust metalloligands in that regard | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Gupta, Sandeep K |e verfasserin |4 aut | |
| 700 | 1 | |a Dechert, Sebastian |e verfasserin |4 aut | |
| 700 | 1 | |a Demeshko, Serhiy |e verfasserin |4 aut | |
| 700 | 1 | |a Duboc, Carole |e verfasserin |4 aut | |
| 700 | 1 | |a Atanasov, Mihail |e verfasserin |4 aut | |
| 700 | 1 | |a Neese, Frank |e verfasserin |4 aut | |
| 700 | 1 | |a Meyer, Franc |e verfasserin |4 aut | |
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| 773 | 1 | 8 | |g volume:63 |g year:2024 |g number:12 |g day:25 |g month:03 |g pages:5652-5663 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.inorgchem.4c00054 |3 Volltext |
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