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

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 (H2L): [Fe3IIIFe2II(HL)6(O)(H 2O)3][ClO4]5·3MeCN· 4H2O, 1, [Co8(HL)8(O)(OH)4(MeOH) 3(H2O)]-[ClO4]3·5MeOH· 2H2O, 2, and [Cu6(Lox)4(MeOH)(H 2O)3]·MeOH, 3. Complex 1 is a mixed valence penta-nuclear iron cluster containing the archetypal {Fe3IIIO} 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, 2, 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 3 contains an oxidised derivative of the ligand, Lox, 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 1-3 reveals dominant antiferro-magnetic interactions for 1 and 2, leading to small non-zero spin ground states, while 3 shows ferro-magnetic exchange between the Cu(ii) centres to give an S = 3 spin ground state. © 2013 The Royal Society of Chemistry.