Linear versus Bent 3d/4f-Heterometallic Clusters: The Carboxylate Effect on the Metal Topology and Magnetic Properties of Two {Mn^III₂Dy₂} Complexes Supported by N-Naphthalidene-o-Aminophenol

Abstract

The initial use of N-naphthalidene-o-aminophenol (naphH 2 ) chelate in heterometallic cluster chemistry has provided access to two chemically similar but structurally dissimilar [Mn III 2 Dy 2 (OMe) 2 (O 2 CR) 6 (naph) 2 ] (R = Me (1), Ph (2)) compounds with rare linear (1) and zigzag (2) topologies, respectively, depending only upon the ancillary carboxylate groups. The "twisted" or "bent"-like structure of 2 has mostly altered the Dy III coordination geometry (square antiprismatic vs triangular dodecahedral in 1), resulting in a slight differentiation of the magnetic dynamics of 2 in comparison with 1. Direct-current (dc) magnetic susceptibility measurements revealed the presence of predominant antiferromagnetic exchange interactions within 1 and 2, while both {Mn III 2 Dy 2 } clusters exhibit out-of-phase (χ″ Μ ), frequency-dependent tails of signals in zero external dc field, characteristic of the onset of the quantum tunneling of magnetization. Attempts to suppress the tunneling through the application of an external dc field were unsuccessful for a wide range of applied fields and alternating-current (ac) frequencies. The combined results demonstrate the ability of the naphH 2 /RCO 2 − "blend" of ligands to yield new heterometallic cluster compounds with appealing structural motifs and potentially interesting magnetic properties.

Construction of A sqc6 Topology Ni‐Gd Framework Employing 2,2’‐Phosphinico‐dibenzoate and Oxalate: Structure and Magnetic Properties

“…These properties always cause the diverse structural variations observed in their compounds. [26][27][28][29] To expand the range of 2,2'-phosphinicodibenzoic acid systems, we incorporated both Ni 2 + and Gd 3 + into the acid framework to generate novel coordination polymers. In 2020, we reported a heterometallic compound, namely [KNi 4 GdL 4 (H 2 O) 8 ] • 14.5H 2 O, where potassium cations bridge each chain to form a 3D framework.…”