A1 Journal article (refereed)
Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes (2017)

Moilanen, J., Mansikkamäki, A., Lahtinen, M., Guo, F.-S., Kalenius, E., Layfield, R. A., & Chibotaru, L. F. (2017). Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes. Dalton Transactions, 46(39), 13582-13589. https://doi.org/10.1039/C7DT02565C

JYU authors or editors

Kalenius, Elina
Moilanen, Jani
Mansikkamäki, Akseli
Lahtinen, Manu

Publication details

All authors or editors: Moilanen, Jani; Mansikkamäki, Akseli; Lahtinen, Manu; Guo, Fu-Sheng; Kalenius, Elina; Layfield, Richard A.; Chibotaru, Liviu F.

Journal or series: Dalton Transactions

ISSN: 1477-9226

eISSN: 1477-9234

Publication year: 2017

Volume: 46

Issue number: 39

Pages range: 13582-13589

Publisher: Royal Society of Chemistry

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1039/C7DT02565C

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/60896

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.

Keywords: coordination complexes; rare earth metals; heat expansion; magnetic properties

Fields of science: