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Tuning of the electronic structure and reactivity of metal complexes with redox-active guanidine ligands

Redox-active ligands change more drastically the electronic structure of metal complexes than non-redox-active ligands, with consequences on the magnetic and optical properties as well as the (redox) reactivity. In this work, redox-active guanidine ligands are integrated in cobalt and copper complex...

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Main Authors: Holzmann, Simone L. (Author) , Osterbrink, Johanna (Author) , Hübner, Olaf (Author) , Schulz, Maximilian (Author) , Poddel'sky, Andrey (Author) , Kaifer, Elisabeth (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: January 13, 2025
In: European journal of inorganic chemistry
Year: 2025, Volume: 28, Issue: 2, Pages: 1-17
ISSN:1099-0682
DOI:10.1002/ejic.202400597
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/ejic.202400597
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.202400597
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Author Notes:Simone L. Holzmann, Johanna Osterbrink, Olaf Hübner, Maximilian Schulz, Andrei Poddelskii, Elisabeth Kaifer, and Hans-Jörg Himmel
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Summary:Redox-active ligands change more drastically the electronic structure of metal complexes than non-redox-active ligands, with consequences on the magnetic and optical properties as well as the (redox) reactivity. In this work, redox-active guanidine ligands are integrated in cobalt and copper complexes. The variations in the electronic structures of cobalt complexes, in particular the relative energies of the states corresponding to high-spin CoII or low-spin CoIII, in dependence of the redox-active o-diguanidine ligand manifest themselves in different magnetic properties. Moreover, the electron transfer rates for copper complexes with two redox-active diguanidino-benzene ligands (self-exchange betweeen a monocationic CuI complex and the corresponding dicationic complex) were varied systematically over two orders of magnitude by choice of the redox-active diguanidine ligand, realizing redox pairs with intermediate or record-high rates.
Item Description:Zuerst veröffentlicht: 26. September 2024
Gesehen am 03.03.2025
Physical Description:Online Resource
ISSN:1099-0682
DOI:10.1002/ejic.202400597

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