A cyano-bridged FeIIReIV(CN)2 cluster incorporating two high-magnetic anisotropy building units

T. David Harris; Han Sen Soo; Christopher J. Chang; Jeffrey R. Long

doi:10.1016/j.ica.2010.12.010

A cyano-bridged Fe^IIRe^IV(CN)₂ cluster incorporating two high-magnetic anisotropy building units

T. David Harris, Han Sen Soo, Christopher J. Chang, Jeffrey R. Long

Chemistry

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

14 Scopus citations

Abstract

The pentagonal bipyramidal high-spin iron(II) complex, [(TPA ^2C(O)NHtBu)Fe(CF₃SO ₃)]⁺, is shown to exhibit a high-anisotropy ground state, with fits to dc magnetization data providing an axial zero-field splitting parameter of D = - 7.9 cm^-1. The utility of this compound as a building unit is demonstrated, as its reaction with [ReCl₄(CN) ₂]^2- affords the cyano-bridged dinuclear cluster (TPA ^2C(O)NHtBu)FeReCl₄(CN)₂. dc magnetic susceptibility measurements reveal intracluster ferromagnetic exchange interactions between Fe^II and Re^IV centers, with J = +3.0 cm^-1, giving rise to a spin ground state of S = 7/2. Moreover, fits to dc magnetization data obtained for the FeRe cluster show the presence of strong axial anisotropy, with D = -2.3 cm^-1. Finally, variable-frequency ac susceptibility measurements reveal the onset of slow magnetic relaxation at low temperature, suggesting that the FeRe cluster is a single-molecule magnet.

Original language	English (US)
Pages (from-to)	91-96
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	369
Issue number	1
DOIs	https://doi.org/10.1016/j.ica.2010.12.010
State	Published - Apr 15 2011

Funding

We thank the Packard foundation (C.J.C.), DOE/LBNL ( 403801 to C.J.C.), and the NSF ( CHE-0617063 to J.R.L.) for funding this work. C.J.C. is an Investigator with the Howard Hughes Medical Institute. We further thank Tyco Electronics for providing T.D.H. with a predoctoral fellowship, H. Harman for helpful discussions, and J. Zadrozny for experimental assistance. Appendix A

Keywords

Cyanide
High-spin iron(II)
Magnetic anisotropy
Single-molecule magnet

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.ica.2010.12.010

Cite this

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title = "A cyano-bridged FeIIReIV(CN)2 cluster incorporating two high-magnetic anisotropy building units",

abstract = "The pentagonal bipyramidal high-spin iron(II) complex, [(TPA 2C(O)NHtBu)Fe(CF3SO 3)]+, is shown to exhibit a high-anisotropy ground state, with fits to dc magnetization data providing an axial zero-field splitting parameter of D = - 7.9 cm-1. The utility of this compound as a building unit is demonstrated, as its reaction with [ReCl4(CN) 2]2- affords the cyano-bridged dinuclear cluster (TPA 2C(O)NHtBu)FeReCl4(CN)2. dc magnetic susceptibility measurements reveal intracluster ferromagnetic exchange interactions between FeII and ReIV centers, with J = +3.0 cm-1, giving rise to a spin ground state of S = 7/2. Moreover, fits to dc magnetization data obtained for the FeRe cluster show the presence of strong axial anisotropy, with D = -2.3 cm-1. Finally, variable-frequency ac susceptibility measurements reveal the onset of slow magnetic relaxation at low temperature, suggesting that the FeRe cluster is a single-molecule magnet.",

keywords = "Cyanide, High-spin iron(II), Magnetic anisotropy, Single-molecule magnet",

author = "Harris, {T. David} and Soo, {Han Sen} and Chang, {Christopher J.} and Long, {Jeffrey R.}",

note = "Funding Information: We thank the Packard foundation (C.J.C.), DOE/LBNL ( 403801 to C.J.C.), and the NSF ( CHE-0617063 to J.R.L.) for funding this work. C.J.C. is an Investigator with the Howard Hughes Medical Institute. We further thank Tyco Electronics for providing T.D.H. with a predoctoral fellowship, H. Harman for helpful discussions, and J. Zadrozny for experimental assistance. Appendix A ",

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AU - Harris, T. David

AU - Soo, Han Sen

AU - Chang, Christopher J.

AU - Long, Jeffrey R.

N1 - Funding Information: We thank the Packard foundation (C.J.C.), DOE/LBNL ( 403801 to C.J.C.), and the NSF ( CHE-0617063 to J.R.L.) for funding this work. C.J.C. is an Investigator with the Howard Hughes Medical Institute. We further thank Tyco Electronics for providing T.D.H. with a predoctoral fellowship, H. Harman for helpful discussions, and J. Zadrozny for experimental assistance. Appendix A

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Y1 - 2011/4/15

N2 - The pentagonal bipyramidal high-spin iron(II) complex, [(TPA 2C(O)NHtBu)Fe(CF3SO 3)]+, is shown to exhibit a high-anisotropy ground state, with fits to dc magnetization data providing an axial zero-field splitting parameter of D = - 7.9 cm-1. The utility of this compound as a building unit is demonstrated, as its reaction with [ReCl4(CN) 2]2- affords the cyano-bridged dinuclear cluster (TPA 2C(O)NHtBu)FeReCl4(CN)2. dc magnetic susceptibility measurements reveal intracluster ferromagnetic exchange interactions between FeII and ReIV centers, with J = +3.0 cm-1, giving rise to a spin ground state of S = 7/2. Moreover, fits to dc magnetization data obtained for the FeRe cluster show the presence of strong axial anisotropy, with D = -2.3 cm-1. Finally, variable-frequency ac susceptibility measurements reveal the onset of slow magnetic relaxation at low temperature, suggesting that the FeRe cluster is a single-molecule magnet.

AB - The pentagonal bipyramidal high-spin iron(II) complex, [(TPA 2C(O)NHtBu)Fe(CF3SO 3)]+, is shown to exhibit a high-anisotropy ground state, with fits to dc magnetization data providing an axial zero-field splitting parameter of D = - 7.9 cm-1. The utility of this compound as a building unit is demonstrated, as its reaction with [ReCl4(CN) 2]2- affords the cyano-bridged dinuclear cluster (TPA 2C(O)NHtBu)FeReCl4(CN)2. dc magnetic susceptibility measurements reveal intracluster ferromagnetic exchange interactions between FeII and ReIV centers, with J = +3.0 cm-1, giving rise to a spin ground state of S = 7/2. Moreover, fits to dc magnetization data obtained for the FeRe cluster show the presence of strong axial anisotropy, with D = -2.3 cm-1. Finally, variable-frequency ac susceptibility measurements reveal the onset of slow magnetic relaxation at low temperature, suggesting that the FeRe cluster is a single-molecule magnet.

KW - Cyanide

KW - High-spin iron(II)

KW - Magnetic anisotropy

KW - Single-molecule magnet

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