Symmetry-breaking substitutions of [Re(CN)8]3- into the centered, face-capped octahedral clusters (CH3OH) 24M9M′6(CN)48 (M = Mn, Co; M′ = Mo, W)

Danna E. Freedman, Miriam V. Bennett, Jeffrey R. Long*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

82 Scopus citations


The diamagnetic complex [Re(CN)8]3- is shown to react with Mn2+ ions in methanol to generate the centered, face-capped octahedral cluster (CH3OH)24Mn9Re 6(CN)48, which is structurally analogous to (CH 3OH)24Mn9Mo6(CN)48. Related reactions involving stoichiometric mixtures of octacyanometalate complexes generate the substituted species (CH3OH) 24Mn9Mo5Re(CN)48, (CH 3OH)24Co9Mo5Re(CN)48, (CH3OH)24Mn9Mo3Re 3(CN)48, (CH3OH)24Mn 9W5Re(CN)48 and (CH3OH) 24Co9W5Re(CN)48, in which the O h symmetry of the cluster core is broken. Reassessment of the magnetic properties of the Mn9Mo6(CN)48 cluster confirm that it possesses a ground state spin of S = 39/2, but does not exhibit single-molecule-magnet behavior. Lowering the symmetry of the molecule by substitutions of ReV at one or three of the MoV sites does not lead to an overall increase in the magnetic anisotropy, as probed by ac magnetic susceptibility measurements. A similar result occurs for the other substituted species, with the important exception of the new single-molecule magnet (CH3OH)24Co9W5Re(CN) 48, for which the spin reversal barrier is significantly reduced relative to that observed previously in (CH3OH)24Co 9W6(CN)48.

Original languageEnglish (US)
Pages (from-to)2829-2834
Number of pages6
JournalDalton Transactions
Issue number23
StatePublished - Jun 15 2006

ASJC Scopus subject areas

  • Inorganic Chemistry


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