Experimental and Computational Study of Unique Tetranuclear µ3-Chloride and µ-Phenoxo/Chloro-Bridged Defective Dicubane Cobalt(II) Clusters

Abstract

Two tetranuclear Co^II clusters [Co₄(L)₂(µ₃-Cl)₂Cl₂] have been prepared by using multidentate diaminobisphenolate ligands. The solid-state structures of the complexes were determined by single-crystal X-ray diffraction. The cores of the cluster compounds can be defined as a two-vertex-deficient dicubane geometry (pseudo-dicubane). In the central unit, the cobalt(II) cations are linked through phenoxide oxygen (outer bridges) and chloride anions (inner bridges), previously unprecedented in this type of cobalt cluster. The magnetic properties were studied by both experimental and computational methods. By using a combination of techniques, we were able to determine the nature and strength of the intramolecular magnetic exchange coupling mediated by the different bridging fragments between the crystallographically different cobalt(II) cations.

Two unique mixed phenoxide/chloride-bridged Co₄ clusters have been prepared by using diaminobisphenolate ligands. The solid-state structures and magnetic-exchange interactions between the Co^II cations have been elucidated by using a combination of experimental and computational techniques.

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