Syntheses, molecular and supramolecular structures, electrochemistry and magnetic properties of two macrocyclic dinickel(II) complexes |
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Authors: | Susanta HazraSuraj Mondal,Michel FleckSujit Sasmal,E. Carolina Sañ udo,Sasankasekhar Mohanta |
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Affiliation: | a Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata 700 009, India b Institute for Mineralogy and Crystallography, University of Vienna, Althanstr, 14, A-1090 Vienna, Austria c Departament de Química Inorgànica i Institut de Nanociència i Nanotecnologia, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain |
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Abstract: | The work in this paper reports syntheses, molecular and supramolecular structures, electrochemistry and magnetic properties of two diphenoxo-bridged dinickel(II) compounds [NiII2L(N3)2(H2O)2]·CH3CN (1) and [NiII2L(N3)2(H2O)] (2), where H2L is the tetraimino diphenolate macrocyclic ligand, obtained on [2 + 2] condensation of 4-methyl-2,6-diformylphenol and 2,2′-dimethyl-1,3-diaminopropane. Brown colored compound 1 and green colored compound 2 are produced from the same reaction mixture as a function of temperature; 1 is formed from the reaction mixture in acetonitrile at low temperature (ca. 5 °C), while 2 is formed on heating the reaction mixture in acetonitrile. Crystals of compounds 1 and 2 are monoclinic (space group P21/c) and orthorhombic (space group P212121), respectively. Analyses of the crystal packing of the crystalline phases reveal that two-dimensional topologies are resulted in both 1 and 2 due to hydrogen bonding interactions. Variable-temperature (2-300 K) magnetic susceptibility measurements of the two compounds reveal that the metal centers in both the complexes are coupled by moderate antiferromagnetic interactions with J values (H = -2JS1·S2) −18.8 and −34.2 cm−1 for 1 and 2, respectively. Electrochemical analyses of 2 reveal that this compound exhibits two-step reduction couples at E½ = −977 and −1155 mV. |
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Keywords: | Macrocyclic Dinuclear Two-dimensional Magnetic properties Electrochemistry Hydrogen bonding |
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