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Royal Society of Chemistry, Dalton Transactions, 37(42), p. 13576, 2013

DOI: 10.1039/c3dt51301g

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Synthesis, structural and magnetic characterisation of iron(II/III), cobalt(II) and copper(II) cluster complexes of the polytopic ligand: N-(2-pyridyl)-3-carboxypropanamide

This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

Herein we describe the synthesis, structural and magnetic characterisation of three transition metal cluster complexes that feature the polytopic ligand N-(2-pyridyl)-3-carboxypropanamide (): [Fe3(III)Fe2(II)(HL)6(O)(H2O)3][ClO4]5·3MeCN·4H2O, , [Co8(HL)8(O)(OH)4(MeOH)3(H2O)]-[ClO4]3·5MeOH·2H2O, , and [Cu6(Lox)4(MeOH)(H2O)3]·MeOH, . Complex is a mixed valence penta-nuclear iron cluster containing the archetypal {Fe3(III)O} triangular basic carboxylate cluster at its core, with two Fe(ii) ions above and below the core coordinated to three bidentate pyridyl-amide groups. The structure of the octanuclear Co(ii) complex, , is based upon a central Co4 square with the remaining four Co(ii) centres at the 'wing-tips' of the complex. The cluster core is replete with bridging oxide, hydroxide and carboxylate groups. Cluster contains an oxidised derivative of the ligand, , generated in situ through hydroxylation of an α-carbon atom. This hexanuclear cluster has a 'barrel-like' core and contains Cu(ii) ions in both square planar and square-based pyramidal geometries. Bridging between Cu(ii) centres is furnished by alkoxide and carboxylate groups. Magnetic studies on reveals dominant antiferro-magnetic interactions for and , leading to small non-zero spin ground states, while shows ferro-magnetic exchange between the Cu(ii) centres to give an S = 3 spin ground state.