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Tri-, Tetra-, and Hexanuclear Copper(II) Phosphonates Containing N-Donor Chelating Ligands: Synthesis, Structure, Magnetic Properties, and Nuclease Activity

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Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India
Departament de Química Inorgànica i, Institut de Nanociència i Nanotecnologia, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain
§ CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe “Matériaux Moléculaires Magnétiques”, 115 avenue du Dr. Albert Schweitzer, Pessac, F-33600, France
Université de Bordeaux, UPR 8641, Pessac, F-33600, France
*To whom correspondence should be addressed. E-mail: [email protected]
Cite this: Inorg. Chem. 2009, 48, 13, 6192–6204
Publication Date (Web):June 5, 2009
https://doi.org/10.1021/ic900522u
Copyright © 2009 American Chemical Society

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    Abstract

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    Reaction of Cu(ClO4)2·6H2O with cyclopentyl phosphonic acid and 2,2′-bipyridine (bpy) in presence of triethylamine afforded a trinuclear compound [Cu3(C5H9PO3)2(bpy)3(MeOH)(H2O)](ClO4)2 (2). The latter dimerizes to a hexanuclear derivative [Cu6(C5H9PO3)4(bpy)6(MeOH)4](ClO4)4 (1) under prolonged reaction conditions. Reaction of CuCl2 with cyclopentyl phosphonic acid and 2,2′-bipyridylamine (bpya) affords a tetranuclear derivative [Cu4(C5H9PO3)2(μ-Cl)2(bpya)4](Cl)2, (MeOH)2 (3). Reaction of the latter with NaClO4 also affords a trinuclear compound [Cu3(C5H9PO3)2(μ-Cl)(bpya)3(H2O)](ClO4) (4). Double and single-bridged hexanuclear species, [{Cu3(C5H9PO3)2(bpy)3(bpp)}(MeOH)2(H2O)(CH2Cl2)(ClO4)2]2 (5), [{Cu3(i-PrPO3)2(bpy)3(4.4′-bpy)(H2O)}(H2O)2(ClO4)2]2 (6), [{Cu3(C5H9PO3)2(bpya)3(4.4′-bpy)(H2O)}(MeOH)(H2O)(ClO4)2]2 (7), and [Cu6(t-BuPO3)4(phen)6(4,4′-bpy)(MeOH)4](CH2Cl2)(H2O)(ClO4)4 (8) (phen = 1,10-phenanthroline) were obtained by the reaction of an in situ generated trinuclear complex with appropriate bridging ligands 4,4′-bipyridine (4,4′-bpy) or 1,3-bis(4-pyridyl)propane (bpp). ESI-MS studies of these complexes reveal that 24 retain their structures in solution. Molecular structures of 28 were determined by X-ray crystallography. All the compounds reveal a capping coordination mode by tridentate phosphonate [RPO3]2− ligands. Detailed magnetic studies on 2 and 48 reveal intramolecular antiferromagnetic interactions between Cu(II) S = 1/2 spins. 2 and 4 are excellent artificial nucleases and can convert supercoiled plasmid DNA (pBR322) into its nicked form without the aid of an external oxidant.

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    Further details are given in Tables S1−S2 and Figures S1−S13. This material is available free of charge via the Internet at http://pubs.acs.org.

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