Inorg Chem. 2015 Mar 16;54(6):2893-901. doi: 10.1021/ic503029t. Epub 2015 Mar 05.

Thermodynamically metastable thiocyanato coordination polymer that shows slow relaxations of the magnetization.

Inorganic chemistry

Julia Werner, Michał Rams, Zbigniew Tomkowicz, Tomče Runčevski, Robert E Dinnebier, Stefan Suckert, Christian Näther

PMID: 25741770 DOI: 10.1021/ic503029t

Abstract

Reaction of cobalt thiocyanate with 4-acetylpyridine leads to the formation of [Co(NCS)2(4-acetylpyridine)2]n (3/I). In its crystal structure the Co cations are connected by pairs of μ-1,3-bridging thiocyanato ligands into dimers that are further connected into layers by single anionic ligands. DTA-TG measurements of Co(NCS)2(4-acetyl-pyridine)4 (1) led to the formation of 3/I. In contrast, when the hydrate Co(NCS)2(4-acetyl-pyridine)2(H2O)2 (2) is decomposed, a mixture of 3/I and a thermodynamically metastable form 3/II is obtained. Further investigations reveal that thermal annealing of 2 leads to the formation of 3/II, that contains only traces of the stable form 3/I. DSC and temperature dependent X-ray powder diffraction (XRPD) measurements prove that 3/II transforms into 3/I on heating. The crystal structure of 3/II was determined ab initio from XRPD data. In its crystal structure the Co cations are linked by pairs of bridging thiocyanato anions into a 1D coordination polymer, and thus, 3/II is an isomer of 3/I. Magnetic measurements disclose that the stable form 3/I only shows paramagnetism without any magnetic anomaly down to 2 K. In contrast, the metastable form 3/II shows ferromagnetic behavior. The phase transition into ordered state at Tc = 3.8 K was confirmed by specific heat measurements. Alternating current susceptibility measurements show frequency dependent maxima in χ' and χ″, which is indicative for a slow relaxation of the magnetization.

Publication Types

• Journal Article