Ln(III)(2)Mn(III)(2) heterobimetallic "butterfly" complexes displaying antiferromagnetic coupling (Ln = Eu, Gd, Tb, Er)

Anthony Chesman, David Roger Turner, Kevin J Berry, Nicholas Frederick Chilton, Boujemaa Moubaraki, Keith Spencer Murray, Glen Berenger Deacon, Stuart Robert Batten

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Abstract

The isostructural heterometallic complexes [Ln(III)(2)Mn(III)(2)O(2)(ccnm)(6)(dcnm)(2)(H(2)O)(2)] (Ln = Eu (1Eu), Gd (1Gd), Tb (1Tb), Er (1Er); ccnm = carbamoylcyanonitrosomethanide; dcnm = dicyanonitrosomethanide) have been synthesised and structurally characterised. The in situ transition metal promoted nucleophilic addition of water to dcnm, forming the derivative ligand ccnm, plays an essential role in cluster formation. The central [Ln(III)(2)Mn(III)(2)(O)(2)] moiety has a butterfly topology. The coordinated aqua ligands and the NH(2) group of the ccnm ligands facilitate the formation of a range of hydrogen bonds with the lattice solvent and neighbouring clusters. Magnetic measurements generally reveal weak intracluster antiferromagnetic coupling, except for the large J(MnMn) value in 1Gd. There is some evidence for single molecule magnetic (SMM) behaviour in 1Er. Comparisons of the magnetic properties are made with other recently reported butterfly-type Ln(III)(x)M(III)(4-x) (d-block) clusters, x = 1, 2; M = Mn, Fe.
Original languageEnglish
Pages (from-to)11402 - 11412
Number of pages11
JournalDalton Transactions
Volume41
Issue number37
DOIs
Publication statusPublished - 2012

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