Chandrasekhar, Vadapalli ; Senapati, Tapas ; Saudo, E. Carolina ; Clerac, R. (2009) Tri-, tetra-, and hexanuclear copper(II) phosphonates containing n-donor chelating ligands: synthesis, structure, magnetic properties, and nuclease activity Inorganic Chemistry, 48 (13). pp. 6192-6204. ISSN 0020-1669
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic900522u
Related URL: http://dx.doi.org/10.1021/ic900522u
Abstract
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 2-4 retain their structures in solution. Molecular structures of 2-8 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 4-8 reveal intramolecular antiferromagnetic interactions between Cu(II) S = ½ 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.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 8923 |
| Deposited On: | 28 Oct 2010 10:33 |
| Last Modified: | 28 Oct 2010 10:33 |
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