Symmetry-based magnetic anisotropy in the trigonal bipyramidal cluster [Tp2(Me3tacn)3Cu3Fe 2(CN)6]4+

Cai Feng Wang; Jing Lin Zuo; Bart M. Bartlett; You Song; Jeffrey R. Long; Xiao Zeng You

doi:10.1021/ja061788+

Symmetry-based magnetic anisotropy in the trigonal bipyramidal cluster [Tp₂(Me₃tacn)₃Cu₃Fe ₂(CN)₆]⁴⁺

Cai Feng Wang, Jing Lin Zuo, Bart M. Bartlett, You Song, Jeffrey R. Long, Xiao Zeng You

College of Chemical Engineering

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

172 Scopus citations

Abstract

Reaction of [(Me₃tacn)Cu(H₂O)₂]₂+ (Me₃tacn = N,N′,N″-trimethyl-1,4,7-triazacyclononane) with [TpFe(CN)₃]^- (Tp^- = hydrotris(pyrazolyl)borate) in a mixture of ethanol and acetonitrile affords the pentanuclear cluster [Tp₂(Me₃tacn)₃Cu₃Fe₂(CN)₆]⁴⁺. Single-crystal X-ray analysis reveals a trigonal bipyramidal structure featuring a D_3h-symmetry core in which two opposing Fe^III (S = 1/2) centers are linked through cyanide bridges to an equatorial triangle of three Cu^II (S = 1/2) centers. Fits to variable-temperature dc magnetic susceptibility data are consistent with ferromagnetic coupling to give an S = 5/2 ground state, while fits to low-temperature magnetization data indicate the presence of a large axial zero-field splitting (D = -5.7 cm^-1). Frequency dependence observed in the ac magnetic susceptibility data confirms single-molecule magnet behavior, with an effective spin reversal barrier of U_eff = 16 cm^-1. When compared with the much lower anisotropy barrier previously observed for the face-centered cubic cluster [Tp₈(H₂O)₆Cu₆Fe₈(CN)₆]⁴⁺, the results demonstrate the enormous influence of the geometry in which a given set of metal ions are arranged.

Original language	English
Pages (from-to)	7162-7163
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	128
Issue number	22
DOIs	https://doi.org/10.1021/ja061788+
State	Published - 7 Jun 2006

Access to Document

10.1021/ja061788+

Cite this

@article{5522f1471bc54752940b1fe99869d265,

title = "Symmetry-based magnetic anisotropy in the trigonal bipyramidal cluster [Tp2(Me3tacn)3Cu3Fe 2(CN)6]4+",

abstract = "Reaction of [(Me3tacn)Cu(H2O)2]2+ (Me3tacn = N,N′,N″-trimethyl-1,4,7-triazacyclononane) with [TpFe(CN)3]- (Tp- = hydrotris(pyrazolyl)borate) in a mixture of ethanol and acetonitrile affords the pentanuclear cluster [Tp2(Me3tacn)3Cu3Fe2(CN)6]4+. Single-crystal X-ray analysis reveals a trigonal bipyramidal structure featuring a D3h-symmetry core in which two opposing FeIII (S = 1/2) centers are linked through cyanide bridges to an equatorial triangle of three CuII (S = 1/2) centers. Fits to variable-temperature dc magnetic susceptibility data are consistent with ferromagnetic coupling to give an S = 5/2 ground state, while fits to low-temperature magnetization data indicate the presence of a large axial zero-field splitting (D = -5.7 cm-1). Frequency dependence observed in the ac magnetic susceptibility data confirms single-molecule magnet behavior, with an effective spin reversal barrier of Ueff = 16 cm-1. When compared with the much lower anisotropy barrier previously observed for the face-centered cubic cluster [Tp8(H2O)6Cu6Fe8(CN)6]4+, the results demonstrate the enormous influence of the geometry in which a given set of metal ions are arranged.",

author = "Wang, {Cai Feng} and Zuo, {Jing Lin} and Bartlett, {Bart M.} and You Song and Long, {Jeffrey R.} and You, {Xiao Zeng}",

year = "2006",

month = jun,

day = "7",

doi = "10.1021/ja061788+",

language = "英语",

volume = "128",

pages = "7162--7163",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Symmetry-based magnetic anisotropy in the trigonal bipyramidal cluster [Tp2(Me3tacn)3Cu3Fe 2(CN)6]4+

AU - Wang, Cai Feng

AU - Zuo, Jing Lin

AU - Bartlett, Bart M.

AU - Song, You

AU - Long, Jeffrey R.

AU - You, Xiao Zeng

PY - 2006/6/7

Y1 - 2006/6/7

N2 - Reaction of [(Me3tacn)Cu(H2O)2]2+ (Me3tacn = N,N′,N″-trimethyl-1,4,7-triazacyclononane) with [TpFe(CN)3]- (Tp- = hydrotris(pyrazolyl)borate) in a mixture of ethanol and acetonitrile affords the pentanuclear cluster [Tp2(Me3tacn)3Cu3Fe2(CN)6]4+. Single-crystal X-ray analysis reveals a trigonal bipyramidal structure featuring a D3h-symmetry core in which two opposing FeIII (S = 1/2) centers are linked through cyanide bridges to an equatorial triangle of three CuII (S = 1/2) centers. Fits to variable-temperature dc magnetic susceptibility data are consistent with ferromagnetic coupling to give an S = 5/2 ground state, while fits to low-temperature magnetization data indicate the presence of a large axial zero-field splitting (D = -5.7 cm-1). Frequency dependence observed in the ac magnetic susceptibility data confirms single-molecule magnet behavior, with an effective spin reversal barrier of Ueff = 16 cm-1. When compared with the much lower anisotropy barrier previously observed for the face-centered cubic cluster [Tp8(H2O)6Cu6Fe8(CN)6]4+, the results demonstrate the enormous influence of the geometry in which a given set of metal ions are arranged.

AB - Reaction of [(Me3tacn)Cu(H2O)2]2+ (Me3tacn = N,N′,N″-trimethyl-1,4,7-triazacyclononane) with [TpFe(CN)3]- (Tp- = hydrotris(pyrazolyl)borate) in a mixture of ethanol and acetonitrile affords the pentanuclear cluster [Tp2(Me3tacn)3Cu3Fe2(CN)6]4+. Single-crystal X-ray analysis reveals a trigonal bipyramidal structure featuring a D3h-symmetry core in which two opposing FeIII (S = 1/2) centers are linked through cyanide bridges to an equatorial triangle of three CuII (S = 1/2) centers. Fits to variable-temperature dc magnetic susceptibility data are consistent with ferromagnetic coupling to give an S = 5/2 ground state, while fits to low-temperature magnetization data indicate the presence of a large axial zero-field splitting (D = -5.7 cm-1). Frequency dependence observed in the ac magnetic susceptibility data confirms single-molecule magnet behavior, with an effective spin reversal barrier of Ueff = 16 cm-1. When compared with the much lower anisotropy barrier previously observed for the face-centered cubic cluster [Tp8(H2O)6Cu6Fe8(CN)6]4+, the results demonstrate the enormous influence of the geometry in which a given set of metal ions are arranged.

UR - http://www.scopus.com/inward/record.url?scp=33744914318&partnerID=8YFLogxK

U2 - 10.1021/ja061788+

DO - 10.1021/ja061788+

M3 - 文章

AN - SCOPUS:33744914318

SN - 0002-7863

VL - 128

SP - 7162

EP - 7163

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 22

ER -

Symmetry-based magnetic anisotropy in the trigonal bipyramidal cluster [Tp₂(Me₃tacn)₃Cu₃Fe ₂(CN)₆]⁴⁺

Abstract

Access to Document

Other files and links

Fingerprint

Cite this