Air-Stable Dinuclear Complexes of Four-Coordinate ZnII and NiII Ions with a Radical Bridge: A Detailed Look at Redox Activity and Antiferromagnetic Coupling.
Inorg Chem
; 63(13): 6042-6050, 2024 Apr 01.
Article
em En
| MEDLINE
| ID: mdl-38502792
ABSTRACT
Air-stable dinuclear complexes [(bmsab)NiII(tmsab)NiII(bmsab)]3- and [(bmsab)ZnII(tmsab)ZnII(bmsab)]3- (bmsab = bis(methanesulfoneamido)benzene, tmsab = tetra(methanesulfonamido)benzene) were prepared via a synthetic route based on heteroleptic precursor complexes. The new complexes combine a distorted tetrahedral coordination environment with an open-shell bridging ligand. The ZnII species was subjected to a detailed investigation of the (spectro-)electrochemical processes. The NiII species is a rare example of a complex that combines strong exchange coupling (J > 440 cm-1) with pronounced positive zero-field splitting (D = +72 cm-1). Combining SQUID magnetometry and (HF)EPR spectroscopy with ab initio calculations allowed for accurate quantification of the exchange interaction.
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MEDLINE
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En
Ano de publicação:
2024
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Article