Slow magnetic relaxation and charge-transfer in cyano-bridged coordination clusters incorporating [Re(CN)(7)](3-/4-).
CLÉRAC, Rodolphe
Université Sciences et Technologies - Bordeaux 1 [UB]
Centre de recherches Paul Pascal [CRPP]
< Reduce
Université Sciences et Technologies - Bordeaux 1 [UB]
Centre de recherches Paul Pascal [CRPP]
Language
en
Article de revue
This item was published in
Inorganic Chemistry. 2010-10-04, vol. 49, n° 19, p. 8886-8896
American Chemical Society
English Abstract
Treatment of the cyanometalate building unit [Re(CN)(7)](3-) with [(PY5Me(2))M(MeCN)](2+) (M = Co, Ni, Cu) affords a series of pentanuclear clusters of formulas [(PY5Me(2))(4)M(4)Re(CN)(7)](5+) (M = Co, Ni, Cu) and ...Read more >
Treatment of the cyanometalate building unit [Re(CN)(7)](3-) with [(PY5Me(2))M(MeCN)](2+) (M = Co, Ni, Cu) affords a series of pentanuclear clusters of formulas [(PY5Me(2))(4)M(4)Re(CN)(7)](5+) (M = Co, Ni, Cu) and [(PY5Me(2))(4)Cu(4)Re(CN)(7)](4+). Single crystal X-ray diffraction analyses of the clusters reveal a star-like structure in which four [(PY5Me(2))M](2+) moieties are linked to a central [Re(CN)(7)](3-) unit via bridging cyanide ligands. An intramolecular Co(II) → Re(IV) charge-transfer accompanies the formation of the Co(II)(4)Re(IV) cluster, giving a Co(II)(3)Co(III)Re(III) species. Spectroelectrochemical methods and irradiation experiments are used to characterize the metal-metal charge-transfer bands of this compound. A rhenium-based thermally induced one-electron reduction is observed for the Cu(II)(4)Re(IV) cluster to give a Cu(II)(4)Re(III) complex; however, this reduction may be forestalled at low temperature. Finally, magnetic measurements reveal intracluster ferromagnetic exchange coupling, strong uniaxial magnetic anisotropy, and slow magnetic relaxation in the Ni(II)(4)Re(IV) and Cu(II)(4)Re(IV) clusters.Read less <
Origin
Hal imported