Synthesis, crystal structure and study of magnetocaloric effect and single molecular magnetic behaviour in discrete lanthanide complexes

Abstract

The synthesis, crystal structure and magnetic properties of four polynuclear lanthanide coordination complexes having molecular formulae, [Gd₃L¹₂(H₂O)₈(Cl)](Cl)₄·10H₂O (1), [Dy₃L¹₂(H₂O)₉](Cl)₅·6H₂O (2) [Gd₆L²₂(HCO₂)₄(μ₃-OH)₄(DMF)₆(H₂O)₂](Cl)₂·4H₂O (3) and [Dy₆L²₂(HCO₂)₄(μ₃-OH)₄(DMF)₆(H₂O)₂](Cl)₂·4H₂O (4) (where H₂L¹ = bis[(2-pyridyl)methylene]pyridine-2,6-dicarbohydrazide and H₄L² = bis[2-hydroxy-benzylidene]pyridine-2,6-dicarbohydrazide) are reported. Structural investigation by X-ray crystallography reveals similar structural features for complexes 1 and 2 and they exhibit butterfly like shapes of the molecules. Non-covalent interactions between the molecules create double helical arrangements for both molecules. Complexes 3 and 4 are isostructural and the core structures feature four distorted hemi-cubanes connected by vertex sharing. Magnetic studies unveil significant magnetic entropy changes for complexes 1, 3 and slow relaxation of magnetization for both dysprosium analogues 2 and 4.