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Issue 39, 2017
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Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes

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Abstract

The synthesis and structural characterization of two benzoquinone-bridged dinuclear rare-earth complexes [BQ(MCl2·THF3)2] (BQ = 2,5-bisoxide-1,4-benzoquinone; M = Y (1), Dy (2)) are described. Of these reported metal complexes, the dysprosium analogue 2 is the first discrete bridged dinuclear lanthanide complex in which both metal centres reside in pentagonal bipyramidal environments. Interestingly, both complexes undergo significant thermal expansion upon heating from 120 K to 293 K as illustrated by single-crystal X-ray and powder diffraction experiments. AC magnetic susceptibility measurements reveal that 2 does not show the slow relation of magnetization in zero dc field. The absent of single-molecule behaviour in 2 arises from the rotation of the principal magnetic axis as compared to the pseudo-C5 axis of the pentagonal bipyramidal environment as suggested by ab initio calculations. The cyclic voltammetry and chemical reduction experiments demonstrated that complexes 1 and 2 can be reduced to radical species containing [BQ3˙]. This study establishes efficient synthetic strategy to make bridged redox-active multinuclear lanthanide complexes with a pentagonal bipyramidal coordination environment that are potential precursors for single-molecule magnets.

Graphical abstract: Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes

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Article information


Submitted
14 Jul 2017
Accepted
18 Sep 2017
First published
18 Sep 2017

Dalton Trans., 2017,46, 13582-13589
Article type
Paper

Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes

J. O. Moilanen, A. Mansikkamäki, M. Lahtinen, F. Guo, E. Kalenius, R. A. Layfield and L. F. Chibotaru, Dalton Trans., 2017, 46, 13582
DOI: 10.1039/C7DT02565C

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