Inorganic Chemistry, Vol.55, No.11, 5237-5244, 2016
Lanthanide-Directed Fabrication of Four Tetranuclear Quadruple Stranded Helicates Showing Magnetic Refrigeration and Slow Magnetic Relaxation
A rare class of four tetranuclear lanthanide based quadruple stranded helicates namely, [Ln(4)L(4)(OH)(2)](OAc)(2)center dot xH(2)O (Ln = Gd-III(1), Dy-III(2) and x = 4, 5 respectively), [Er4L4(OH)(2)](NO3)(2)center dot 9H(2)O (3), and [Dy4L4(NO3)](NO3)(2)center dot 2CH(3)OH center dot H2O (4) were synthesized by employing succinohydrazone derived bis-tridentate ligand (H2L) and characterized. Structures of 1-3 are similar to each other except the nature of counterions and number of lattice water molecules. In 4, a distorted nitrate ion was arranged in a hexagonal manner holding four dysprosium centers in a slightly twisted manner. Because of the symmetrical nature of each complex, the C-4 axis crosses the center of helicate resulting a pseudo-D-4 coordination environment. Each ligand coordinates to lanthanide centers in helical manner forming mixture of left (Lambda) and right (Delta) handed discrete units. Complex 1 exhibits antiferromagnetic exchange interaction between nearby Gd-III centers and shows magnetic refrigeration (-Delta S-m = 24.4 J kg(-1) K-1 for Delta H = 7 T at 3 K). AC magnetic susceptibility measurements of 2 and 4 demonstrate slow relaxation behavior, with U-eff (effective energy barrier) of 20.5 and 4.6 K, respectively. As per our knowledge, complexes 1, 2, and 4 represent the first examples of aesthetically pleasing quadruple stranded helicates showing potential magnetocaloric effect and single-molecule-magnet-like behavior.