Effect of ligand substituents on supramolecular self-assembly and electrochemical properties of copper(II) complexes with benzoylhydrazones: X-ray crystal structures and cyclic voltammetry
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文摘
Complexation of copper(II) with a series of hetero-donor chelating Schiff bases (HLLR) of para-substituted benzhydrazides (with R = OH, NO2, CH3O, Cl and tert-butyl substituents) and acetone affords mononuclear [Cu(LLR)2] molecules: 1 [Cu(anbhz)2] (R = NO2); 2 [Cu(ahbhz)2] (R = OH) 3 [Cu(ambhz)2] (R = CH3O); 4 [Cu(acbhz)2] (R = Cl); and 5 [Cu(atbhz)2] (R = tert-butyl). Single-crystal X-ray diffraction results for 2-5 reveal their various supramolecular architectures including 1D and 2D dimensionalities. A detailed analysis of crystal structures allows to gain insight into intermolecular interactions accountable for self-assembly into different networks as well as for various physicochemical properties of the compounds. The major interactions include O-H?N hydrogen bonds (2) as well as CH?N and axial Cu?O (3); ¦Ð?¦Ð stacking (4) and van der Waals CH?C interactions (5). All compounds are characterized by elemental analyses; IR and UV-Vis spectroscopy as well as magnetic susceptibility and cyclic voltammetry measurements. Electrochemical studies reveal the dependence of [Cu(LLR)2]/[Cu(LLR)2]?/sup> reduction potentials on substituents of benzoylhydrazonoate ligands.
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