Octahedral Copper(II) Carboxylates with 1,10-Phenanthroline: Synthesis, Structural Characterization, DNA-Binding and Ant
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ORIGINAL PAPER
Octahedral Copper(II) Carboxylates with 1,10‑Phenanthroline: Synthesis, Structural Characterization, DNA‑Binding and Anti‑Fungal Properties Muhammad Iqbal1 · Saqib Ali2 · Muhammad N. Tahir3 · Paul A. Anderson4 Received: 16 April 2019 / Accepted: 29 September 2020 © Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract Two mono-nuclear axially distorted octahedral copper(II) complexes have been prepared and characterized via FT-IR, UV–Visible, elctrochemical, electron spin resonance and powder and single crystal XRD techniques. The complexes consist of a phenanthroline and two carboxylate ligands each bonded in bidentate fashion. Carboxylates are ortho-nitro-2-phenyl acetate (L1) and para-chloro-2-phenyl acetate (L2). Structural study showed that both complexes possess Jahn–Teller distorted octahedral geometry. The bulk purity was assessed from the matching experimental and simulated powder XRD spectra. The results of spectroscopic techniques are consistent with each other. ESR data revealed single electron occupancy of dx2 − y2 orbital with 2B1g as ground state typical of tetragonally distorted octahedral geometry. Electrochemical solution study showed diffusion controlled electron transfer processes with diffusion co-efficient values of 10.323 × 10–8 cm2s–1 and 0.972 × 10–8 cm2s–1 for 1 and 2. Complexes exhibited excellent DNA-binding activity studied via UV–Visible spectroscopy, cyclic voltammetry, florescence spectroscopy and viscometry yielding K b values of 1.871 × 104 M–1 (1) and 1.577 × 104 M–1 4 –1 4 –1 6 –1 (2), 0.38 × 10 M (1) and 6.39 × 10 M (2) and 2.1 × 10 M (1) and 2.0 × 06 M–1 (2), respectively, for the first three techniques. Complexes possess good antifungal activity against three fungal strains. Graphic Abstract
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0.05 0.00 -0.05 -0.10 -0.15 -0.6
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0.6
E/V
Keywords Copper(ii) carboxylates · Structural description · Electrochemistry · DNA binding study · Anti-fungal study
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13
Vol.:(0123456789)
Journal of Chemical Crystallography
Introduction
Experimental
Copper carboxylate complexes with 1,10-phenanthroline exhibit variety of structures. Mononuclear carboxylates possess octahedral as well as square pyramidal geometry depending upon the coordination mode of carboxylate ligands. Some mono-nuclear carboxylates possess single phenanthroline unit while others possess two units [1, 2]. The geometry around copper in dinuclear carboxylates having phenanthroline ligands is mostly square pyramidal [3, 4] where each copper ion is coordinated by a phenanthroline ligand in usual bidentate fashion. In this type, variable number of carboxylate ligands are attached to the copper ions. The most common form contains four carboxylate units and two phenanthroline ligands, the former bonded in mono-dentate fashion to copper ions [3]. Some dinuclear carboxylates possess carboxylate moieties uncoordinated, lying in crystal lattice, while the coordination v
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