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Issue 4, 2017
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Influence of metal coordination and co-ligands on the magnetic properties of 1D Co(NCS)2 coordination polymers

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Abstract

Two new transition metal thiocyanate coordination polymers with the composition [Co(NCS)2(4-vinylpyridine)2]n (1) and [Co(NCS)2(4-benzoylpyridine)2]n (2) were synthesized and their crystal structures were determined. In both compounds the Co cations are octahedrally coordinated by two trans-coordinating 4-vinyl- or 4-benzoylpyridine co-ligands and four μ-1,3-bridging thiocyanato anions and linked into chains by the anionic ligands. While in 1 the N and the S atoms of the thiocyanate anions are also in trans-configuration, in 2 they are in cis-configuration. A detailed magnetic study showed that the intra-chain ferromagnetic coupling is slightly stronger for 2 than for 1, and that the chains in both compounds are weekly antiferromagnetically coupled. Both compounds show a long range magnetic ordering transition at Tc = 3.9 K for 1 and Tc = 3.7 K for 2, which is confirmed by specific heat measurements. They also show a metamagnetic transition at a critical field of 450 Oe (1) and 350 Oe (2), respectively. Below Tc1 and 2 exhibit magnetic relaxations resembling relaxations of single chains. The exchange constants obtained from magnetic and specific heat data are in good accordance with those obtained from constrained DFT calculations carried out on isolated model systems. The ab initio calculations allowed us to find the principal directions of anisotropy.

Graphical abstract: Influence of metal coordination and co-ligands on the magnetic properties of 1D Co(NCS)2 coordination polymers

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Supplementary files

Article information


Submitted
30 Nov 2016
Accepted
19 Dec 2016
First published
20 Dec 2016

This article is Open Access

Phys. Chem. Chem. Phys., 2017,19, 3232-3243
Article type
Paper

Influence of metal coordination and co-ligands on the magnetic properties of 1D Co(NCS)2 coordination polymers

M. Rams, Z. Tomkowicz, M. Böhme, W. Plass, S. Suckert, J. Werner, I. Jess and C. Näther, Phys. Chem. Chem. Phys., 2017, 19, 3232
DOI: 10.1039/C6CP08193B

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