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

Russell, Mark E.; Hawes, Chris S.; Ferguson, Alan; Polson, Matthew I. J.; Chilton, Nicholas F.; Moubaraki, Boujemaa; Murray, Keith S.; Kruger, Paul E.

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 (H2222L): [Fe3IIIFe2II(HL)6(O)(H2O)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)(H2O)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, Loxox, 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.

Citation

Russell, M. E., Hawes, C. S., Ferguson, A., Polson, M. I. J., Chilton, N. F., Moubaraki, B., …Kruger, P. E. (2013). 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. Dalton Transactions, 42(37), 13576. https://doi.org/10.1039/c3dt51301g

• Journal Article Type: Article
• Acceptance Date: Jul 19, 2013
• Online Publication Date: Jul 9, 2013
• Publication Date: 2013
• Deposit Date: Jun 16, 2023
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 42
• Issue: 37
• Pages: 13576
• DOI: https://doi.org/10.1039/c3dt51301g
• Keywords: Inorganic Chemistry