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One-pot reactions of an asymmetric carboxy-ether-phenol based Schiff base H 2 L (2-((2-hydroxy-3-methoxybenzylidene)amino)benzoic acid) with selected Ln(NO 3 ) 3 · n H 2 O and [Co 2 (μ-OH 2 )(O 2 CCMe 3 ) 4 (HO 2 CCMe 3 ) 4 ] ( Co   2   -Piv ) in basic MeOH medium resulted in a family of three octanuclear complexes, [Co II  4 Ln III  4 L 4 (μ 1,3 -Piv) 4 (μ 1,1,3 -Piv) 2 (η 1 -Piv) 2 (μ 3 -OH) 4 (MeOH) 2 ]· m MeOH· n H 2 O (Ln = Dy; m = 3, n = 1 ( 1 ), Ho; m = 4, n = 0 ( 2 ), Yb; m = 3, n = 1 ( 3 )). The coordination aggregates thus obtained were nicely sustained by four ligand anions and eight externally added carboxylate anions showing three different modes of intermetallic connectivity. The options for incorporating different 4f ions in an investigative synthesis, without altering the resulting intermetallic core structure, were successful for the three representative examples. Single-crystal X-ray diffraction studies revealed that the compounds are isostructural and built from two initially formed partial dicubane-type Co 2 Ln 2 L 2 units. In each of the tetranuclear parts, the metal ion centers are held together by two L 2  - , two μ 3 -HO - , three Piv - bridges, one terminal Piv - , and one terminal MeOH. Four carboxylate ends of four L 2  - units are responsible for connecting two Co 2 Ln 2 units into octanuclear structures. The unique distortion around the Co II centers is achieved from the facile coordination of bigger 4f ions to the adjacent hard OO sites. The distortion is further maintained by the presence of terminal COO - groups from L 2  - . The dc magnetic susceptibility data revealed ferromagnetic coupling between the Co II and Ln III centers within the series, whereas the ac magnetic susceptibility measurements identified only 1 , having a highly anisotropic Dy III ion, as a single-molecule magnet in the absence of any external magnetic field, with an energy barrier U  eff of 12.5 K.

inorganic chemistry

Carboxylate-Decorated Aggregation of Octanuclear Co<sub>4</sub>Ln<sub>4</sub> (Ln = Dy, Ho, Yb) Complexes from Ligand-Controlled Hydrolysis: Synthesis, Structures, and Magnetic Properties

Carboxylate-Decorated Aggregation of Octanuclear Co4Ln4 (Ln = Dy, Ho, Yb) Complexes from Ligand-Controlled Hydrolysis: Synthesis, Structures, and Magnetic Properties

Carboxylate-Decorated Aggregation of Octanuclear Co₄Ln₄ (Ln = Dy, Ho, Yb) Complexes from Ligand-Controlled Hydrolysis: Synthesis, Structures, and Magnetic Properties