Structure and magnetism of a mixed-valence octanuclear manganese(II/III) cluster derived from carbamoylcyanonitrosomethanide (ccnm)

A mixed-valence octanuclear manganese complex of formula [Mn(II)(4)Mn(III)(4)O(4)(ccnm)(12)]·4MeCN·7H(2)O (1·4MeCN·7H(2)O) (ccnm = carbamoylcyanonitrosomethanide) has been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and magnetic measurements...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2013-01, Vol.42 (5), p.1400-1405
Main Authors: Razali, Mohd R, Chesman, Anthony S R, Chilton, Nicholas F, Langley, Stuart K, Moubaraki, Boujemaa, Murray, Keith S, Deacon, Glen B, Batten, Stuart R
Format: Article
Language:English
Subjects:
Clusters
Cubane
Diffraction
Displays
Distortion
Infrared radiation
Magnetism
X-rays
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Summary:A mixed-valence octanuclear manganese complex of formula [Mn(II)(4)Mn(III)(4)O(4)(ccnm)(12)]·4MeCN·7H(2)O (1·4MeCN·7H(2)O) (ccnm = carbamoylcyanonitrosomethanide) has been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and magnetic measurements. The metal core of 1 adopts a tetra-capped (with Mn(II) ions) distorted [Mn(III)(4)O(4)](4+) cubane topology, with a three-J magnetic analysis indicating that the cluster displays dominant antiferromagnetic interactions. Three equally possible fits were obtained, all leading to a spin ground state of S = 0 with S = 1, 2 and 3 close in energy. Comparisons of the magnetic analysis are made with that published for a related Mn(8) cluster and, more generally, with other Mn(III)Mn(III) and Mn(III)Mn(II) fragments in clusters of various types.
ISSN:1477-9226
1477-9234
DOI:10.1039/c2dt32303f