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Synthesis, crystal structures and magnetic properties of a 1D chain based on trinuclear Cu subunits and a Cu4Dy2 complex

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Abstract A one-dimensional (1D) chain [Cu3(HL)2(N3)(Mtta)]n.0.5CH3CN (1, H3L = 2-((2-hydroxybenzylidene)amino)propane-1,3-diol and Mtta = 5-methyl tetrazolate) and a Cu4Dy2 complex [Cu4Dy2{(py)2CO2}2{(py)2C(OH)O}2(CH3COO)4(N3)4].3CH3CN (2, (py)2C(OH)2 = the gem-diol form of di-2-pyridyl ketone) were obtained by the assemblies of the… Click to show full abstract

Abstract A one-dimensional (1D) chain [Cu3(HL)2(N3)(Mtta)]n.0.5CH3CN (1, H3L = 2-((2-hydroxybenzylidene)amino)propane-1,3-diol and Mtta = 5-methyl tetrazolate) and a Cu4Dy2 complex [Cu4Dy2{(py)2CO2}2{(py)2C(OH)O}2(CH3COO)4(N3)4].3CH3CN (2, (py)2C(OH)2 = the gem-diol form of di-2-pyridyl ketone) were obtained by the assemblies of the H3L ligand and Dy(NO3)3·5H2O with copper nitrate or with copper acetate and di-2-pyridyl ketone under the MeCN solution containing triethylamine or containing NaOH. In 1, three CuII ions were linked into a trinuclear Cu unit by three neighboring N atoms of Mtta ligand and two alkoxido-type O atoms from two HL2− ligands, then these units were further linked into a one-dimensional (1D) chain by two phenoxido O atoms from two HL2− ligands. In 2, two CuII and two DyIII ions formed a butterfly-type topology, which was further linked another two CuII by the O atoms from (py)2CO22– or from acetate ligands. Magnetic studies indicated that, in 1, the magnetic coupling through the paths of Cu N N Cu and Cu-Oalkoxido-Cu is antiferromagnetic (J1 = −14.81 cm−1), and its value was first determined in the polynuclear Cu complexes containing Mtta ligand. However, the magnetic coupling through the path of Cu-Ophenoxido-Cu is ferromagnetic (J2 = 24.61 cm−1). Magnetic studies revealed that 1 exhibits slow magnetic relaxation behavior, with an energy barrier Ueff of 6.06 K. The orientations of the easy magnetization axes of DyIII ions in 2 was estimated by Magellan program, indicating that the easy axes of DyIII in 2 are roughly aligned along alkoxido-type O atoms (O3 and O3a), which is slightly longer than other Dy-O distances.

Keywords: chain; structures magnetic; synthesis crystal; cu4dy2 complex; crystal structures; magnetic properties

Journal Title: Inorganica Chimica Acta
Year Published: 2021

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