A redox-switchable single-molecule magnet incorporating [Re(CN) 7]3-

Danna E. Freedman; David M. Jenkins; Anthony T. Iavarone; Jeffrey R. Long

doi:10.1021/ja077527x

A redox-switchable single-molecule magnet incorporating [Re(CN) ₇]^3-

Danna E. Freedman, David M. Jenkins, Anthony T. Iavarone, Jeffrey R. Long

Chemistry

Research output: Contribution to journal › Article › peer-review

239 Scopus citations

Abstract

Reaction of [Re(CN)₇]^3- (S = 1/2) with 4 equiv of [(PY5Me₂)Mn(MeCN)]²⁺ (S = 5/2) in acetonitrile generates a blue solution containing the cyano-bridged cluster [(PY5Me₂)₄Mn₄Re(CN)₇]⁵⁺. At room temperature, the color of the reaction rapidly changes from blue to green to yellow, spontaneously generating the one-electron reduced species [(PY5Me₂)₄Mn₄Re(CN)₇]⁴⁺. Crystal structures show these two clusters share a star-like geometry, wherein four [(PY5Me₂)Mn]²⁺ units are appended to a central, pentagonal bipyramidal [Re(CN)₇]^3-/4- complex. The dc magnetic properties of the 5+ cluster indicate the presence of ferromagnetic coupling to give an S = 21/2 ground state with an axial zero-field splitting of D = -0.44 cm^-1. Ac magnetic susceptibility measurements reveal a spin relaxation barrier of Ueff = 33 cm^-1, the largest barrier yet observed for a cyano-bridged single-molecule magnet. Upon reduction by one electron, the spin at the Re center is lost and the cluster switches behavior to that of a simple paramagnet containing four noncoupled MnII centers.

Original language	English (US)
Pages (from-to)	2884-2885
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	130
Issue number	10
DOIs	https://doi.org/10.1021/ja077527x
State	Published - Mar 12 2008

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "A redox-switchable single-molecule magnet incorporating [Re(CN) 7]3-",

abstract = "Reaction of [Re(CN)7]3- (S = 1/2) with 4 equiv of [(PY5Me2)Mn(MeCN)]2+ (S = 5/2) in acetonitrile generates a blue solution containing the cyano-bridged cluster [(PY5Me2)4Mn4Re(CN)7]5+. At room temperature, the color of the reaction rapidly changes from blue to green to yellow, spontaneously generating the one-electron reduced species [(PY5Me2)4Mn4Re(CN)7]4+. Crystal structures show these two clusters share a star-like geometry, wherein four [(PY5Me2)Mn]2+ units are appended to a central, pentagonal bipyramidal [Re(CN)7]3-/4- complex. The dc magnetic properties of the 5+ cluster indicate the presence of ferromagnetic coupling to give an S = 21/2 ground state with an axial zero-field splitting of D = -0.44 cm-1. Ac magnetic susceptibility measurements reveal a spin relaxation barrier of Ueff = 33 cm-1, the largest barrier yet observed for a cyano-bridged single-molecule magnet. Upon reduction by one electron, the spin at the Re center is lost and the cluster switches behavior to that of a simple paramagnet containing four noncoupled MnII centers.",

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AU - Iavarone, Anthony T.

AU - Long, Jeffrey R.

PY - 2008/3/12

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N2 - Reaction of [Re(CN)7]3- (S = 1/2) with 4 equiv of [(PY5Me2)Mn(MeCN)]2+ (S = 5/2) in acetonitrile generates a blue solution containing the cyano-bridged cluster [(PY5Me2)4Mn4Re(CN)7]5+. At room temperature, the color of the reaction rapidly changes from blue to green to yellow, spontaneously generating the one-electron reduced species [(PY5Me2)4Mn4Re(CN)7]4+. Crystal structures show these two clusters share a star-like geometry, wherein four [(PY5Me2)Mn]2+ units are appended to a central, pentagonal bipyramidal [Re(CN)7]3-/4- complex. The dc magnetic properties of the 5+ cluster indicate the presence of ferromagnetic coupling to give an S = 21/2 ground state with an axial zero-field splitting of D = -0.44 cm-1. Ac magnetic susceptibility measurements reveal a spin relaxation barrier of Ueff = 33 cm-1, the largest barrier yet observed for a cyano-bridged single-molecule magnet. Upon reduction by one electron, the spin at the Re center is lost and the cluster switches behavior to that of a simple paramagnet containing four noncoupled MnII centers.

AB - Reaction of [Re(CN)7]3- (S = 1/2) with 4 equiv of [(PY5Me2)Mn(MeCN)]2+ (S = 5/2) in acetonitrile generates a blue solution containing the cyano-bridged cluster [(PY5Me2)4Mn4Re(CN)7]5+. At room temperature, the color of the reaction rapidly changes from blue to green to yellow, spontaneously generating the one-electron reduced species [(PY5Me2)4Mn4Re(CN)7]4+. Crystal structures show these two clusters share a star-like geometry, wherein four [(PY5Me2)Mn]2+ units are appended to a central, pentagonal bipyramidal [Re(CN)7]3-/4- complex. The dc magnetic properties of the 5+ cluster indicate the presence of ferromagnetic coupling to give an S = 21/2 ground state with an axial zero-field splitting of D = -0.44 cm-1. Ac magnetic susceptibility measurements reveal a spin relaxation barrier of Ueff = 33 cm-1, the largest barrier yet observed for a cyano-bridged single-molecule magnet. Upon reduction by one electron, the spin at the Re center is lost and the cluster switches behavior to that of a simple paramagnet containing four noncoupled MnII centers.

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A redox-switchable single-molecule magnet incorporating [Re(CN) ₇]^3-

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