ZADROZNY, Joseph M.; FREEDMAN, Danna E.; JENKINS, David M.; HARRIS, T. David; IAVARONE, Anthony T.; MATHONIÈRE, Corine; CLÉRAC, Rodolphe; LONG, Jeffrey R.

doi:10.1021/ic101132z

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ZADROZNY, Joseph M.
Department of Chemistry [Berkeley]

FREEDMAN, Danna E.
Department of Chemistry [Berkeley]

JENKINS, David M.
Department of Chemistry [Berkeley]
Department of Chemistry

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Inorganic Chemistry. 2010-10-04, vol. 49, n° 19, p. 8886-8896

American Chemical Society

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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.< Réduire

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Slow magnetic relaxation and charge-transfer in cyano-bridged coordination clusters incorporating [Re(CN)(7)](3-/4-).

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