Air-Stable Dinuclear Complexes of Four-Coordinate ZnII and NiII Ions with a Radical Bridge: A Detailed Look at Redox Activity and Antiferromagnetic Coupling

Simon Suhr; David Hunger; Robert R M Walter; Andreas Köhn; Joris van Slageren; Biprajit Sarkar

doi:10.1021/acs.inorgchem.4c00351

Air-Stable Dinuclear Complexes of Four-Coordinate Zn^II and Ni^II Ions with a Radical Bridge: A Detailed Look at Redox Activity and Antiferromagnetic Coupling

Inorg Chem. 2024 Apr 1;63(13):6042-6050. doi: 10.1021/acs.inorgchem.4c00351. Epub 2024 Mar 19.

Authors

Simon Suhr¹, David Hunger², Robert R M Walter¹, Andreas Köhn³, Joris van Slageren², Biprajit Sarkar¹

Affiliations

¹ Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart 70569, Germany.
² Institut für Physikalische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart 70569, Germany.
³ Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart 70569, Germany.

PMID: 38502792
DOI: 10.1021/acs.inorgchem.4c00351

Abstract

Air-stable dinuclear complexes [(bmsab)Ni^II(tmsab)Ni^II(bmsab)]^3- and [(bmsab)Zn^II(tmsab)Zn^II(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 Zn^II species was subjected to a detailed investigation of the (spectro-)electrochemical processes. The Ni^II 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.