Fine tuning of the redox-active diguanidine ligand in cationic cobalt complexes for electronic structure control
In this work we show that the redox chemistry of hexacoordinated cobalt complexes with redox-active diguanidine ligands could be tuned by modifying the diguanidine and/or the co-ligands. In this way, one-electron oxidation could be directed to be either ligand- or metal-centered, leading to high-spi...
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| Hauptverfasser: | , , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
August 2, 2025
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| In: |
Chemistry - a European journal
Year: 2025, Jahrgang: 31, Heft: 51, Pages: 1-15 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.202501382 |
| Online-Zugang: | Verlag, kostenfrei, Volltext: https://doi.org/10.1002/chem.202501382 Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202501382 
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| Verfasserangaben: | Johanna Osterbrink, Meret Kaliske, Maximilian Schulz, Hanna Koepcke, Olaf Hübner, Elisabeth Kaifer, and Hans-Jörg Himmel |
MARC
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| 245 | 1 | 0 | |a Fine tuning of the redox-active diguanidine ligand in cationic cobalt complexes for electronic structure control |c Johanna Osterbrink, Meret Kaliske, Maximilian Schulz, Hanna Koepcke, Olaf Hübner, Elisabeth Kaifer, and Hans-Jörg Himmel |
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| 520 | |a In this work we show that the redox chemistry of hexacoordinated cobalt complexes with redox-active diguanidine ligands could be tuned by modifying the diguanidine and/or the co-ligands. In this way, one-electron oxidation could be directed to be either ligand- or metal-centered, leading to high-spin CoII complexes with an oxidized, radical-monocationic diguanidine ligand (ligand-centered oxidation) or low-spin CoIII complexes with a reduced, neutral diguanidine ligand. Further fine-tuning of the redox-active diguanidine ligand leads to a harmonization of the energies of both redox isomers. Consequently, ligand- as well as metal-centered one-electron oxidation is observed, resulting in a mixture of both redox isomers. Quantum-chemical calculations confirm the energetic proximity of the two redox isomers in this bistable system. The results of this work contribute to the development of a directed approach toward the design of bistable cobalt-guanidine complexes and their possible applications in spin-switching devices. | ||
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| 650 | 4 | |a electronic structure | |
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| 650 | 4 | |a redox-active ligand | |
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