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Determination of the relevant magnetic interactions in low-dimensional molecular materials: the fundamental role of single crystal high frequency EPR (Articolo in rivista)

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Determination of the relevant magnetic interactions in low-dimensional molecular materials: the fundamental role of single crystal high frequency EPR (Articolo in rivista) (literal)

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Allao, Rafael Alves; Jordao, Alessandro K.; Resende, Jackson A. L. C.; Cunha, Anna C.; Ferreira, Vitor F.; Novak, Miguel A.; Sangregorio, Claudio; Sorace, Lorenzo; Vaz, Maria G. F. (2011)
Determination of the relevant magnetic interactions in low-dimensional molecular materials: the fundamental role of single crystal high frequency EPR
in Dalton transactions (2003. Print)
(literal)

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Allao, Rafael Alves; Jordao, Alessandro K.; Resende, Jackson A. L. C.; Cunha, Anna C.; Ferreira, Vitor F.; Novak, Miguel A.; Sangregorio, Claudio; Sorace, Lorenzo; Vaz, Maria G. F. (literal)

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[Allao, Rafael Alves; Sangregorio, Claudio; Sorace, Lorenzo] Univ Florence, Dipartimento Chim U Schiff, I-50019 Florence, Italy; Univ Florence, INSTM Res Unit, I-50019 Florence, Italy. [Allao, Rafael Alves; Jordao, Alessandro K.; Resende, Jackson A. L. C.; Cunha, Anna C.; Ferreira, Vitor F.; Vaz, Maria G. F.] Univ Fed Fluminense, Inst Quim, BR-24020141 Niteroi, RJ, Brazil. [Novak, Miguel A.] Univ Fed Rio de Janeiro, Inst Fis, BR-21941972 Rio De Janeiro, Brazil. [Sangregorio, Claudio] CNR ISTM Milano, I-20133 Milan, Italy. (literal)

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Determination of the relevant magnetic interactions in low-dimensional molecular materials: the fundamental role of single crystal high frequency EPR (literal)

Abstract

A new one-dimensional copper(II) complex with formula [Cu(hfac)(2)(N(3)TEMPO)](n) (hfac = hexafluoroacetylacetonate and N(3)TEMPO = 4-azido-2,2,6,6-tetramethylpiperidine-1-oxyl) has been synthesized and investigated by X-ray crystallography, magnetometry and multifrequency single crystal EPR. The system crystallizes in the P (1) over bar space group with two non equivalent copper(II) ions in the unit cell, the two nitroxide radicals being coordinated to Cu(1) in axial positions. The copper(II) ions are bridged by N(3)TEMPO radicals resulting in a zig-zag chain structure. The magnetic susceptibility data were at first satisfactorily modeled assuming an alternating spin chain along the monodimensional covalent skeleton, with a ferromagnetic interaction between Cu(1) and the nitroxide moieties and a weaker antiferromagnetic interaction between these and Cu(2) (J(1) = -13.8 cm(-1), J(2) = +2.4 cm(-1)). However, single crystal EPR studies performed at the X-and W-band clearly demonstrate that the observed magnetic monodimensional character of the complex is actually due to the intermolecular contacts involving N(3)TEMPO ligands. This prompted us to fit the magnetic data using a consistent model, pointing out the fundamental role of single crystal EPR data in defining a correct model to describe the magnetic properties of molecular low dimensional systems. (literal)

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