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Synthesis, structures and magnetic properties of tetranuclear heterometallic complexes [Cu3M] (M = Mn(II) Co(II) and Ni(II)) based on an oxamido-bridged ligand


Three tetranuclear heterometallic coordination compounds of the general formula [(CuL)2M(CuL·CH3OH)](ClO4)2 [(M = Mn(for 2), Co(for 3) and Ni(for 4)] were synthesized by the reaction of the precursor CuL·0.5H2O (1) (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,12-diphenyl-1,4,8,11-tetraazacyclotetradeca-7,12-diene) with M(ClO4)2·6H2O under solvothermal conditions. The compounds were fully characterized by elemental analysis, FTIR, UV–Vis spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction analysis. In addition, compound 2–4 were studied by magnetic susceptibility measurements. All three heterometallic compounds are isomorphous, and the central ions Mn(II), Co(II) and Ni(II) are connected to three CuL fragments via exo-cis oxamido bridges. Magnetic susceptibility studies of complexes 2–4 indicate the occurrence of antiferromagnetic coupling between the paramagnetic metals. The experimental data have been fitted according to the following Heisenberg Hamiltonian \(\hat{H} = - 2J\hat{S}_{{\text{M}}} (\hat{S}_{{{\text{Cu}}1}} + \hat{S}_{{{\text{Cu}}2}} + \hat{S}_{{{\text{Cu}}3}} )\), leading to J = − 15.24 cm−1, gCu = 2.06, gMn = 1.96 for complex 2, J = − 22.58 cm−1, gCu = 2.1, gCo = 2.55 for complex 3, and J = − 108.2 cm−1, gCu = 2.09, gNi = 2.27 for complex 4, respectively.

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The work was supported by National Natural Science Foundation of China (21761026); Natural Science Foundation of Inner Mongolia (2016BS0206); Inner Mongolia Autonomous Region Higher Scientific Research Project (NJZY18020); Collaborative Innovation Center for Water Environmental Security of Inner Mongolia Autonomous Region (XTCX003).

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Zhang, YH., Deng, GR. & Gao, YY. Synthesis, structures and magnetic properties of tetranuclear heterometallic complexes [Cu3M] (M = Mn(II) Co(II) and Ni(II)) based on an oxamido-bridged ligand. Transit Met Chem 44, 737–745 (2019).

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