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

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 (-U(eff)/k(B)) of 62.5 K for the spin relaxation.