Unusually Distorted Pseudo-Octahedral Coordination Environment Around CoII from Thioether Schiff Base Ligands in Dinuclear [CoLn] (Ln = La, Gd, Tb, Dy, Ho) Complexes: Synthesis, Structure, and Understanding of Magnetic Behavior.

The synthesis, structural characterization, and magnetic behavior of a new family of binuclear CoII-LnIII complexes of formula [LnIIICoIIL2(NO3)3]·H2O (Ln = La, 1; Gd, 2; Tb, 3; Dy, 4; Ho, 5; HL = 3-methoxy-N-(2-(methylsulfanyl)phenyl)salicylaldimine) have been reported. The chosen ligand system HL has adjacent soft ONS and hard OO binding pockets ideal for selective coordination of CoII and 4f metal ions. All the complexes 1-5 exhibit a CoII center in a highly distorted octahedral geometry with the LnIII centers in bicapped square-antiprism geometry. The unique distortion about the CoII center is introduced by the coordination of 4f metal ions in the hard OO coordination site. The distortion is further supported by the presence of -SMe groups giving an S donor atom which owing to its larger size can support large bond distances and angles. The geometry around the CoII centers is intermediate between meridional and facial geometric isomers. The magnetic properties of these complexes have been investigated by a "full model" approach using CONDON with the experimental magnetochemical analysis revealing ferromagnetic Co-Ln coupling in compounds 2-5. Ab initio calculations on the X-ray crystal structures of 1-5 paint a semiquatitative picture about the contribution of the individual anisotropic centers toward the overall magnetic properties of the compounds. Theoretical analysis predicts 1 and 2 as weak single-ion magnet (SIM) and single-molecule magnet (SMM) respectively with CoII being solely responsible for the complex anisotropy. In 2, JCoGd plays a crucial role in preserving the anisotropy contribution of Co by channelizing relaxation via a higher excited exchange doublet. Because of the inefficiency of JCoTb, JCoDy, and JCoHo in quenching single-ion Ln fragment transverse anisotropy and preserving CoII high axial anisotropy (favoring rhombicity), 3-5 lack SMM behavior.