Entrapment of a Pseudo-Tetrahedral CoII Center by Thioether Sulfur Bound {Co2 (μ-L)} Fragments: Synthesis, Field-Induced Single-Ion Magnetism and Catechol Oxidase Mimicking Activity.

Simultaneous incorporation of both CoII and CoIII ions within a new thioether S-bearing phenol-based ligand system, H3 L (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) formed [Co5 ] aggregates [CoII CoIII 4 L2 (μ-OH)2 (μ1,3 -O2 CCH3 )2 ](ClO4 )4 ⋅H2 O (1) and [CoII CoIII 4 L2 (μ-OH)2 (μ1,3 -O2 CC2 H5 )2 ](ClO4 )4 ⋅H2 O (2). The magnetic studies revealed axial zero-field splitting (ZFS) parameter, D/hc=-23.6 and -24.3 cm-1 , and E/D=0.03 and 0.00, respectively for 1 and 2. Dynamic magnetic data confirmed the complexes as SIMs with Ueff /kB =30 K (1) and 33 K (2), and τ0 =9.1×10-8  s (1), and 4.3×10-8  s (2). The larger atomic radius of S compared to N gave rise to less variation in the distortion of tetrahedral geometry around central CoII centers, thus affecting the D and Ueff /kB values. Theoretical studies also support the experimental findings and reveal the origin of the anisotropy parameters. In solutions, both 1 and 2 which produce {CoIII 2 (μ-L)} units, display solvent-dependent catechol oxidation behavior toward 3,5-di-tert-butylcatechol in air. The presence of an adjacent CoIII ion tends to assist the electron transfer from the substrate to the metal ion center, enhancing the catalytic oxidation rate.