The key role of hydrogen bonding in the nuclearity of three copper(II) complexes with hydrazone-derived ligands and nitrogen donor heterocycles |
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Authors: | Shyamapada Shit Corrado Rizzoli Guillaume Pilet Samiran Mitra |
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Affiliation: | a Department of Chemistry, Jadavpur University, Kolkata 700 032, West Bengal, India b Department of Chemistry, Bankura Sammilani College, Kenduadihi, Bankura 722 102, West Bengal, India c Università degli Studi di Parma, Dip. di Chimica GIAF, Viale G.P. Usberti 17/A, I-43100 Parma, Italy d Università degli Studi di Trieste, Dip. di Scienze Chimiche e Farmaceutiche, Via Licio Giorgieri, 1, 34127 Trieste, Italy e Groupe de Cristallographie et Ingénierie Moléculaire, Laboratoire des Multimatériaux et Interfaces, UMR 5615, Université Claude Bernard Lyon 1, Bât. Jules Roulin, 43 Bd du 11 Novembre, 1918-69622 Villeurbanne Cedex, France f Instituto de Ciencia Molecular, ICMol, Universidad de Valencia, Parque Científico, 46980 Paterna, Spain |
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Abstract: | Three new Cu(II) complexes of formula [Cu(L1)(pyz)(CH3OH)]ClO4 (1), [Cu(L1)(4,4′-bpy)(ClO4)]·0.5H2O (2) and [{Cu(L2)(ClO4)}2(μ-4,4′-bpy)] (3) have been synthesised by using pyrazine (pyz) and 4,4′-bipyridine (4,4′-bpy) and tridentate O,N,O-donor hydrazone ligands, L1H and L2H, obtained by the condensation of 1,1,1-trifluoro-2,4-pentanedione with salicyloylhydrazide and benzhydrazide, respectively. The ligands and their complexes have been characterized by elemental analyses, FT-IR, and UV-Vis spectroscopies. Single crystal X-ray structure analysis evidences the metal ion in a slightly deformed square pyramidal geometry in all the complexes. However complexes 1 and 2 are mononuclear with pyz and 4,4′-bpy, respectively, showing an unusual monodentate behavior, while complex 3 is dinuclear with 4,4′-bpy adopting the typical bridging coordination mode. Self assembly of the complex units by hydrogen bonding interactions produces one-dimensional arrangement in each crystal packing. The magnetic characterization of complex 3 indicates a weak antiferromagnetic exchange interaction between the Cu(II) ions (J = −0.96 cm−1) mediated through the long 4,4′-bpy bridge. Electrochemical behavior of the complexes is also discussed. |
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Keywords: | Cu(II) hydrazone complexes Crystal structures Monodentate pyz and 4,4&prime -bpy Self assembly Hydrogen bonding Antiferromagnetic coupling |
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