Structures and magnetic properties of MnIII4LnIII4 aggregates with a “square-in-square” topology

Valeriu Mereacre; Muhammad Nadeem Akhtar; Yanhua Lan; Ayuk M. Ako; Rodolphe Clérac; Christopher E. Anson; Annie K. Powell

doi:10.1039/B926899E

Structures and magnetic properties of Mn^III₄Ln^III₄ aggregates with a “square-in-square” topology†‡

Valeriu Mereacre,^a Muhammad Nadeem Akhtar,^a Yanhua Lan,^a Ayuk M. Ako,^ab Rodolphe Clérac,^cd Christopher E. Anson^a and Annie K. Powell*^ab

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* Corresponding authors

^a Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstr. 15, Karlsruhe, Germany
E-mail: annie.powell@kit.edu
Fax: +49-721-608-8142
Tel: +49-721-608-2135

^b Institute of Nanotechnology, Karlsruhe Institute of Technology, Postfach 3640, Karlsruhe, Germany

^c CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe "Matériaux Moléculaires Magnétiques", 115 avenue du Dr Albert Schweitzer, Pessac, France

^d Université de Bordeaux, UPR 8641, Pessac, France

Abstract

The structures and magnetic properties of a family of new octanuclear heterometallic 3d-4f complexes [Mn^III₄Ln^III₄(μ₃-OH)₄(μ₂,η¹-X)₄(O₂CBu^t)₈(t-bdea)₄]·solv, where X = N₃⁻, Ln = Y (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); X = OCN⁻, Ln = Dy (7); X = NO₃⁻, Ln = Gd (8), Tb (9), Dy (10), Ho (11), Er (12); solv = MeCN or toluene, are reported. The metal topology in the aggregates can be described as consisting of a “Ln₄-square inscribed in a Mn₄-square”. Complexes 1-7 are prepared by the reactions of t-butyldiethanolamine (t-bdeaH₂) with a preformed hexanuclear manganese pivalate complex [Mn₆], the respective lanthanide salt and either NaN₃ or NaNCO, while 8-12 are obtained from the direct reaction of Mn(OAc)₂, Ln(NO₃)₃·xH₂O and t-butyldiethanolamine. The magnetic properties of all the complexes were investigated using variable temperature magnetic susceptibility and magnetisation measurements. Similar magnetic behaviour was observed for compounds containing the same lanthanide, indicating that changing the bridging ligand X does not have a significant effect on the magnetic behaviour. The Tb^III and Dy^III compounds 4, 5, 7, 9 and 10 all show frequency-dependent ac susceptibilities indicative of a slow relaxation of magnetisation and are therefore considered as Single-Molecule Magnets.

This article is part of the themed collection: Molecular magnets

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Article information

DOI: https://doi.org/10.1039/B926899E
Article type: Paper
Submitted: 22 Dec 2009
Accepted: 05 Mar 2010
First published: 19 Apr 2010

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Dalton Trans., 2010,39, 4918-4927

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Structures and magnetic properties of Mn^III₄Ln^III₄ aggregates with a “square-in-square” topology

V. Mereacre, M. N. Akhtar, Y. Lan, A. M. Ako, R. Clérac, C. E. Anson and A. K. Powell, Dalton Trans., 2010, 39, 4918 DOI: 10.1039/B926899E

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