Crystal Structure and Magnetic Properties of Trinuclear Transition Metal Complexes (MnII, CoII, NiII and CuII) with Bridging Sulfonate-Functionalized 1,2,4-Triazole Derivatives

Abstract

Here we present the synthesis, structure and magnetic properties of complexes of general formula (Mn)(Me2NH2)4][Mn3(μ-L)6(H2O)6] and (Me2NH2)6[M3(μ-L)6(H2O)6] (M = CoII, NiII and CuII); L−2 = 4-(1,2,4-triazol-4-yl) ethanedisulfonate). The trinuclear polyanions were isolated as dimethylammonium salts, and their crystal structures determined by single crystal and powder X-ray diffraction data. The polyanionic part of these salts have the same molecular structure, which consists of a linear array of metal(II) ions linked by triple N1-N2-triazole bridges. In turn, the composition and crystal packing of the MnII salt differs from the rest of the complexes (with six dimethyl ammonia as countercations) in containing one Mn+2 and four dimethyl ammonia as countercations. Magnetic data indicate dominant intramolecular antiferromagnetic interactions stabilizing a paramagnetic ground state. Susceptibility data have been successfully modeled with a simple isotropic Hamiltonian for a centrosymmetric linear trimer, H = −2J (S1S2 + S2S3) with super-exchange parameters J = −0.4 K for MnII, −7.5 K for NiII and −45 K for CuII complex. The magnetic properties of these complexes and their easy processing opens unique possibilities for their incorporation as magnetic molecular probes into such hybrid materials as magnetic/conducting multifunctional materials or as dopant for organic conducting polymers.

Sulfur-center Reactivity toward Oxygenation Mediated by Ruthenium: Effective Bioactive Compounds (A Review)

“…Alongside this there are another S-oxygenated compound termed metal-sulfonate [M-SO 3 -] can be isolable. 46 Metal-thiolates to metal-sulfenato, metalsulfinato conversion by the incorporation of molecular oxygen is two electron and four electron oxidation process respectively. 47 In general metal-sulfenates are less stable than the corresponding metal-sulfinates and would disproportionate to metal-thiolate and metal-sulfinates, although a few examples of stable transition metal sulfenates [M-(S(=O)R)] are known.…”

Two pillared-layer metal–organic frameworks based on the pinwheel trinuclear carboxylate-clusters of Zn(ii) and Co(ii): synthesis, crystal structures, magnetic study, and Lewis acid catalysis

“…46 47 Finally, there are many recent reports on the high values of magnetic susceptibility observed for MOFs with Co(II) clusters. [48][49][50] In this work, two 3D MOFs, Zn-MOF and Co-MOF, were designed using linear 4,4′-dicarboxylic acid (H 2 L1) and imine functionalized bis( pyridyl)-phenylene-di-imine (L2) ligands (Scheme 1). Ligand H 2 L1 is chosen to construct such M-O-M bridges for the development of polynuclear MOFs with higher net junctions.…”

“…47 Finally, there are many recent reports on the high values of magnetic susceptibility observed for MOFs with Co( ii ) clusters. 48–50…”