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Issue 45, 2010
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Solid-state transformation of [Co(NCS)2(pyridine)4] into [Co(NCS)2(pyridine)2]n: from Curie–Weiss paramagnetism to single chain magnetic behaviour

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Abstract

Reaction of Co(NCS)2 with pyridine (pyr) in aqueous solution at room temperature leads to the formation of the pyridine-rich 1 : 4 compound of composition [Co(NCS)2(pyridine)4] (1) reported recently. On heating, the pyridine-rich 1 : 4 compound transforms into its corresponding pyridine-deficient 1 : 2 compound of composition [Co(NCS)2(pyridine)2]n (2), which decomposes on further heating. In the crystal structure of compound 2 the metal cations are coordinated by four N-atoms of two pyridine ligands and two N-bonded thiocyanato anions, each in mutually trans orientation, and by two S-atoms of two adjacent thiocyanato anions in a slightly distorted octahedral geometry. The thiocyanato anions bridge the metal cations forming one-dimensional polymeric chains. IR spectroscopic investigations on the pyridine-deficient 1 : 2 compound prepared in thermal decomposition are in accordance with bridging thiocyanato anions. Magnetic measurements of the pyridine-rich 1 : 4 compound and pyridine-deficient 1 : 2 compound reveal different behaviour with Curie–Weiss paramagnetism for compound 1 and single chain magnetic behaviour for compound 2, with a Mydosh-parameter φ = 0.12 and an effective energy barrier (−Ueff/kB) of 62.5 K for the spin relaxation.

Graphical abstract: Solid-state transformation of [Co(NCS)2(pyridine)4] into [Co(NCS)2(pyridine)2]n: from Curie–Weiss paramagnetism to single chain magnetic behaviour

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Publication details

The article was received on 23 Jul 2010, accepted on 10 Sep 2010 and first published on 14 Oct 2010


Article type: Paper
DOI: 10.1039/C0DT00904K
Citation: Dalton Trans., 2010,39, 11019-11026
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    Solid-state transformation of [Co(NCS)2(pyridine)4] into [Co(NCS)2(pyridine)2]n: from Curie–Weiss paramagnetism to single chain magnetic behaviour

    J. Boeckmann and C. Näther, Dalton Trans., 2010, 39, 11019
    DOI: 10.1039/C0DT00904K

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