6533b7d4fe1ef96bd1261d2a

RESEARCH PRODUCT

Family of Isomeric CuII–LnIII (Ln = Gd, Tb, and Dy) Complexes Presenting Field-Induced Slow Relaxation of Magnetization Only for the Members Containing GdIII

Tanmoy Kumar GhoshSouvik MaityAshutosh GhoshAshutosh GhoshJúlia Mayans

subject

LanthanideField (physics)010405 organic chemistryChemistryRelaxation (NMR)010402 general chemistry01 natural sciences0104 chemical sciencesInorganic ChemistryMagnetizationCrystallographyMagnetic anisotropyMagnetic relaxationPhysical and Theoretical ChemistryIsostructuralTemplate method pattern

description

The strategic design and synthesis of two isomeric CuII complexes, [CuLA] and [CuLB], of asymmetrically dicondensed N2O3-donor Schiff-base ligands (where H2LA and H2LB are N-salicylidene-N'-3-methoxysalicylidenepropane-1,2-diamine and N-3-methoxysalicylidene-N'-salicylidenepropane-1,2-diamine, respectively) have been accomplished via a convenient CuII template method. These two complexes have been used as metalloligands for the synthesis of three pairs of Cu-Ln isomeric complexes [CuL(μ-NO3)Ln(NO3)2(H2O)]·CH3CN (for complexes 1A-3A, L = LA, and for complexes 1B-3B, L = LB and Ln = Gd, Tb, and Dy, respectively), all of which have been characterized structurally. In all six isomorphous and isostructural complexes, the decacoordinated LnIII centers and pentacoordinated CuII centers possess sphenocorona and square-pyramidal geometries, respectively. The isomeric pair of Cu-Gd compounds shows field-induced slow relaxation of magnetization, although they present the typical isotropic behavior of GdIII complexes, indicating that slow relaxation is not due to the usual energy barrier originating from the magnetic anisotropy. The isostructural derivatives with the ion-anisotropic lanthanides TbIII and DyIII do not show slow magnetic relaxation with or without a direct-current bias field, demonstrating that the magnetic response of the isotropic system CuII-GdIII occurs through different mechanisms than the rest of the Ln cations.

https://doi.org/10.1021/acs.inorgchem.0c03129