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Structural Variations in (CuL)2Ln Complexes of a Series of Lanthanide Ions with Salen-Type Unsymmetrical Schiff Base(H2L): The Dy and Tb Derivatives as Potential Single-Molecule Magnets

Abstract

A new series of heterometallic trinuclear Cu2Ln complexes [lanthanoid ions Ln = Gd (1), Tb (2), Dy (3), Ho (4) and Er (5)] has been synthesized using a Cu(II)-metalloligand derived from a N2O2 donor unsymmetrical Schiff base, H2L (where H2L = N--methylsalicylidene-N΄-salicylidene-1,3-propanediamine) and structurally characterized. Among these complexes, [(CuL)2Gd(NO3)3(CH3CN)2] (1), [(CuL)2Tb(NO3)3(CH3CN)2] (2) and [(CuL)2Dy(NO3)3(CH3CN)2] (3) are isomorphic and isostructural. In these complexes two metalloligands coordinate to the central Ln(III) (Ln= Gd, Tb and Dy respectively) ion in a transoid fashion via μ2-phenoxido oxygen atoms. The Ln(III) ions are deca-coordinated with distorted tetradecahedron geometry. The two terminal Cu(II) ions of the complexes possess hexa-coordinated distorted octahedral geometry. In contrast, complexes [(CuL)2Ho(NO3)3 (CH3CN)], (4) and [(CuL)2Er(NO3)3(CH3CN)]•0.5(CH3CN) (5), two metalloligands coordinated to Ln(III)ions in a cisoid fashion. The Ho(III) ion in 4 is nona-coordinated with distorted tricapped-trigonal prism geometry and the Er(III) ion in 5 is octa-coordinated with a distorted square antiprismatic geometry. The two terminal Cu(II) ions in complex 4 and 5 are penta-coordinated with a distorted square-pyramidal geometry. The dc magnetic susceptibilities and field dependent magnetization measurement of complex 1 reveal the occurrence of ferromagnetic interaction between Cu(II) and Gd(III) ions as well as intermolecular antiferromagnetic interaction. Both complexes 2 and 3 show ferromagnetic interactions between Cu(II) and Ln(III) ions, but in case of 4 and 5 antiferromagnetic interactions are observed . The ac magnetic susceptibilities of all the complexes were also recorded and it was found that only complexes 2 and 3 exhibit slow relaxation of magnetization reorientation below 10 K at 2000 Oe applied dc field, being characteristics of single molecule magnets (SMMs).

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Publication details

The article was received on 06 Jun 2017, accepted on 10 Aug 2017 and first published on 10 Aug 2017


Article type: Paper
DOI: 10.1039/C7DT02061A
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Structural Variations in (CuL)2Ln Complexes of a Series of Lanthanide Ions with Salen-Type Unsymmetrical Schiff Base(H2L): The Dy and Tb Derivatives as Potential Single-Molecule Magnets

    P. Mahapatra, S. Ghosh, N. Koizumi, T. Kanetomo, T. Ishida, M. G.B Drew and A. Ghosh, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT02061A

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