Tetranuclear Manganese Complex Incorporating 2‐Pyridyloximate Ligand: Synthesis, Crystal Structure and Magnetic Property

Abstract

A tetranuclear manganese complex of the composition {Mn4[(Py)C(Ph)NO]4(CH3CH2OH)3(CH3CH2O)Cl3}·2H2O (1) was synthesized by solvothermal reaction, and characterized by X‐ray single crystal diffraction, IR spectroscopy, and elemental analysis. X‐ray analysis revealed that complex 1 contains a [Mn4(NO)4]4+ core with three MnII atoms displaying distorted octahedral arrangements and one MnII ion exhibiting a trigonal bipyramidal arrangement. Low‐temperature magnetic susceptibility measurement for the solid sample of 1 revealed antiferromagnetic MnII···MnII interactions.

Manganese clusters derived from 2-pyridylcyanoxime: new topologies and a large spin ground state in pyridyloximate chemistry

“…As was previously observed in Cu II and Ni II chemistry, manganese derivatives of pyC(CN)NOH exhibit different structural trends than other pyridyloximates. Oximate clusters containing exclusively Mn II are rare and have only been characterized for the pyC(H)NOH ligand in two hexanuclear clusters 4,27 and one decanuclear 5 cluster and for one tetranuclear 28 system derived from pyC(Ph)NOH. Syntheses of 1 and 2a were performed in methanol and this slightly reductor solvent seems to better stabilize the low-valent manganese oxidation state than the other pyridyloximates.…”

“…The low J values obtained for compounds 1 and 2a agree with those reported in previous compounds with oximate bridges between divalent manganese cations which exhibit weak antiferromagnetic coupling. 4,5,27,28 The temperature dependence of the χ M T product for compound 3 is plotted in Fig. 7.…”