Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S = 5 ground state

Paul Cooper; Floriana Tuna; Muralidharan Shanmugam; Lorenzo Sorace; Sarah L. Heath; David Collison; Eric J L McInnes; Richard E P Winpenny

doi:10.1016/j.ica.2008.03.081

Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S = 5 ground state

Paul Cooper, Floriana Tuna, Muralidharan Shanmugam, Lorenzo Sorace, Sarah L. Heath, David Collison, Eric J L McInnes, Richard E P Winpenny

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

Abstract

The synthesis, crystal structure and magnetic properties of the hexametallic Fe(III) cluster [Fe6III O2 (OH)2 {(C4 N2 H2 SMe)2 C (OH) O}2 (t BuCO2)10] (1) are reported. Compound 1 was prepared by reaction of mixed-valent [Fe3O(tBuCO2)6(py) 3] with one equivalent of the new ligand di-2-(4-methylthio)pyrimidyl ketone (DTPK) in MeCN solution. Compound 1 consists of a planar array of six Fe(III) ions comprising two [Fe3(μ3-O)]7+ subunits that are related by an inversion centre and linked at two of their apices, each via one μ-hydroxide and two μ-carboxylate groups. Variable temperature magnetic susceptibility and low temperature magnetization measurements show a well isolated S = 5 electronic spin ground state. Variable temperature W-band EPR measurements on a polycrystalline sample give well resolved spectra and simulations confirm a negative zero-field splitting of D = -0.224 cm-1 but also reveal a very rhombic nature (E/|D| = 0.27). Although 1 has a well isolated S = 5 ground state with a negative magnetic anisotropy, it is not a SMM due to this large rhombicity. © 2008 Elsevier B.V. All rights reserved.

Original language	English
Pages (from-to)	3663-3668
Number of pages	5
Journal	Inorganica Chimica Acta
Volume	361
Issue number	12-13
DOIs	https://doi.org/10.1016/j.ica.2008.03.081
Publication status	Published - 1 Sept 2008

Keywords

HF-EPR
High spin ground states
Iron clusters
Magnetic studies

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10.1016/j.ica.2008.03.081

CCDC 702005: Experimental Crystal Structure Determination
Cooper, P. (Contributor), Tuna, F. (Contributor), Shanmugam, M. (Contributor), Sorace, L. (Contributor), Heath, S. (Contributor), Collison, D. (Contributor), Mcinnes, E. (Contributor) & Winpenny, R. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2009
DOI: 10.5517/ccrkhb3, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccrkhb3&sid=DataCite
Dataset

Cite this

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title = "Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S = 5 ground state",

abstract = "The synthesis, crystal structure and magnetic properties of the hexametallic Fe(III) cluster [Fe6III O2 (OH)2 {(C4 N2 H2 SMe)2 C (OH) O}2 (t BuCO2)10] (1) are reported. Compound 1 was prepared by reaction of mixed-valent [Fe3O(tBuCO2)6(py) 3] with one equivalent of the new ligand di-2-(4-methylthio)pyrimidyl ketone (DTPK) in MeCN solution. Compound 1 consists of a planar array of six Fe(III) ions comprising two [Fe3(μ3-O)]7+ subunits that are related by an inversion centre and linked at two of their apices, each via one μ-hydroxide and two μ-carboxylate groups. Variable temperature magnetic susceptibility and low temperature magnetization measurements show a well isolated S = 5 electronic spin ground state. Variable temperature W-band EPR measurements on a polycrystalline sample give well resolved spectra and simulations confirm a negative zero-field splitting of D = -0.224 cm-1 but also reveal a very rhombic nature (E/|D| = 0.27). Although 1 has a well isolated S = 5 ground state with a negative magnetic anisotropy, it is not a SMM due to this large rhombicity. {\textcopyright} 2008 Elsevier B.V. All rights reserved.",

keywords = "HF-EPR, High spin ground states, Iron clusters, Magnetic studies",

author = "Paul Cooper and Floriana Tuna and Muralidharan Shanmugam and Lorenzo Sorace and Heath, {Sarah L.} and David Collison and McInnes, {Eric J L} and Winpenny, {Richard E P}",

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T1 - Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S = 5 ground state

AU - Cooper, Paul

AU - Tuna, Floriana

AU - Shanmugam, Muralidharan

AU - Sorace, Lorenzo

AU - Heath, Sarah L.

AU - Collison, David

AU - McInnes, Eric J L

AU - Winpenny, Richard E P

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N2 - The synthesis, crystal structure and magnetic properties of the hexametallic Fe(III) cluster [Fe6III O2 (OH)2 {(C4 N2 H2 SMe)2 C (OH) O}2 (t BuCO2)10] (1) are reported. Compound 1 was prepared by reaction of mixed-valent [Fe3O(tBuCO2)6(py) 3] with one equivalent of the new ligand di-2-(4-methylthio)pyrimidyl ketone (DTPK) in MeCN solution. Compound 1 consists of a planar array of six Fe(III) ions comprising two [Fe3(μ3-O)]7+ subunits that are related by an inversion centre and linked at two of their apices, each via one μ-hydroxide and two μ-carboxylate groups. Variable temperature magnetic susceptibility and low temperature magnetization measurements show a well isolated S = 5 electronic spin ground state. Variable temperature W-band EPR measurements on a polycrystalline sample give well resolved spectra and simulations confirm a negative zero-field splitting of D = -0.224 cm-1 but also reveal a very rhombic nature (E/|D| = 0.27). Although 1 has a well isolated S = 5 ground state with a negative magnetic anisotropy, it is not a SMM due to this large rhombicity. © 2008 Elsevier B.V. All rights reserved.

AB - The synthesis, crystal structure and magnetic properties of the hexametallic Fe(III) cluster [Fe6III O2 (OH)2 {(C4 N2 H2 SMe)2 C (OH) O}2 (t BuCO2)10] (1) are reported. Compound 1 was prepared by reaction of mixed-valent [Fe3O(tBuCO2)6(py) 3] with one equivalent of the new ligand di-2-(4-methylthio)pyrimidyl ketone (DTPK) in MeCN solution. Compound 1 consists of a planar array of six Fe(III) ions comprising two [Fe3(μ3-O)]7+ subunits that are related by an inversion centre and linked at two of their apices, each via one μ-hydroxide and two μ-carboxylate groups. Variable temperature magnetic susceptibility and low temperature magnetization measurements show a well isolated S = 5 electronic spin ground state. Variable temperature W-band EPR measurements on a polycrystalline sample give well resolved spectra and simulations confirm a negative zero-field splitting of D = -0.224 cm-1 but also reveal a very rhombic nature (E/|D| = 0.27). Although 1 has a well isolated S = 5 ground state with a negative magnetic anisotropy, it is not a SMM due to this large rhombicity. © 2008 Elsevier B.V. All rights reserved.

KW - HF-EPR

KW - High spin ground states

KW - Iron clusters

KW - Magnetic studies

U2 - 10.1016/j.ica.2008.03.081

DO - 10.1016/j.ica.2008.03.081

M3 - Article

SN - 0020-1693

VL - 361

SP - 3663

EP - 3668

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 12-13

ER -

Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S = 5 ground state

Abstract

Keywords

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CCDC 702005: Experimental Crystal Structure Determination

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