Metal-Organic Frameworks as Playgrounds for Reticulate Single-Molecule Magnets

Achieving fine control on the structure of metal-organic frameworks (MOFs) is mandatory to obtain target physical properties. Herein, we present how the combination of a metalloligand approach and a postsynthetic method is a suitable and highly useful synthetic strategy to success on this extremely difficult task. First, a novel oxamato-based tetranuclear cobalt(III) compound with a tetrahedron-shaped geometry is used, for the first time, as the metalloligand toward calcium(II) metal ions to lead to a diamagnetic Ca^II-Co^III three-dimensional (3D) MOF (1). In a second stage, in a single-crystal-to-single-crystal manner, the calcium(II) ions are replaced by terbium(III), dysprosium(III), holmium(III), and erbium(III) ions to yield four isostructural novel Ln^III-Co^III [Ln = Tb (2), Dy (3), Ho (4), and Er (5)] 3D MOFs. Direct-current magnetic properties for 2-5 show typical performances for the ground-state terms of the lanthanoid cations [⁷F₆ (Tb^III), ⁶H_15/2 (Dy^III), ⁵I₈ (Ho^III), and ⁴I_15/2 (Er^III)]. Analysis of the χ_MT data indicates that the ground state is the lowest M value, that is, M = 0 (2 and 4) and ±¹/₂ (3 and 5). Kramers' ions (3 and 5) exhibit field-induced emergent frequency-dependent alternating-current magnetic susceptibility signals, which is indicative of the presence of slow magnetic relaxation typical of single-molecule magnets.