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., Murray, K. S., & 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
• Public URL: https://keele-repository.worktribe.com/output/471798