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Issue 4, 2007
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The contrasted structural and magnetic behaviour of two single-component paramagnetic dithiolene complexes

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Abstract

The neutral organometallic/dithiolene radical complexes [CpNi(oxddt)] and [CpNi(bddt)] were prepared, respectively, from the reactions of [Ni(oxddt)2] with [Cp2Ni] and (NBu4)[Ni(bddt)2] with [CpNi(cod)](BF4) (oxddt = o-xylenediyldithioethylene-1,2-dithiolato, bddt = 1,4-butanediyldithioethylene-1,2-dithiolato). Both complexes exhibit reversible oxidation and reduction waves to the cation and anion forms, respectively. A NIR absorption is observed around λmax = 825 for [CpNi(oxddt)] and 774 nm for [CpNi(bddt)] in dichloromethane solution. The X-ray crystal structures of the two complexes show two-legged piano-stool geometries around the central nickel atom (formally NiIII) and strong distortions from planarity of the eight-membered ring moieties. In the solid state, the stronger rigidity of [CpNi(oxddt)] allows for a face-to-face π–π stacking of the radicals into dyads, confirmed by a singlet–triplet magnetic behaviour while the more flexible [CpNi(bddt)] radical complexes only interact through a lateral antiferromagnetic interaction giving rise to Heisenberg-type uniform spin chains.

Graphical abstract: The contrasted structural and magnetic behaviour of two single-component paramagnetic dithiolene complexes

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Article information


Submitted
09 Jan 2007
Accepted
22 Feb 2007
First published
19 Mar 2007

New J. Chem., 2007,31, 528-534
Article type
Paper

The contrasted structural and magnetic behaviour of two single-component paramagnetic dithiolene complexes

M. Nomura and M. Fourmigué, New J. Chem., 2007, 31, 528
DOI: 10.1039/B700278E

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