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Issue 9, 2016
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The solvent effect on the structural and magnetic features of bidentate ligand-capped {CoII9[WV(CN)8]6} single-molecule magnets

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Abstract

Cyanido-bridged {CoII9[WV(CN)8]6} Single-Molecule Magnets grow spontaneously from the methanolic solution of Co2+ and [WV(CN)8]3− ions. Here, these molecules were combined with the 2,2′-bipyridine N-oxide (2,2′-bpmo) ligand resulting in three novel crystalline phases: {CoII[CoII(2,2′-bpmo)(MeOH)]6[CoII(2,2′-bpmo)(MeCN)]2[WV(CN)8]6}·8H2O·2MeCN·2MeOH (1) and {CoII[CoII(2,2′-bpmo)(MeOH)]8[WV(CN)8]6}·H2O·8.5MeCN·11.5MeOH (2) which grow from the MeOH–MeCN solution, and {CoII[CoII(2,2′-bpmo)(EtOH)]8[WV(CN)8]6}·3H2O·5.5MeCN·5EtOH (3) which crystallizes from the EtOH–MeCN mixture. They are constructed by {CoII9WV6} clusters of a six-capped body-centered cube topology, coordinating 2,2′-bpmo ligands at the external CoII sites. 1–3 exhibit different composition and geometrical arrangement in their outer fac-[CoII(μ-NC)3(2,2′-bpmo)(solvent)] moieties, and different solvent organization in the intercluster space. This results in a well pronounced geometrical isomerism of cluster cores being further related to the diverse non-covalent interaction schemes governing the supramolecular arrangement of the molecules. 1, 2, and 3 reveal ferromagnetic coupling within Co–NC–W linkages leading to a high-spin ground state of 15/2, and slow magnetic relaxation at low temperatures. The single-molecule magnet characteristics are only slightly modulated by the solvent-dependent variation of the structural features.

Graphical abstract: The solvent effect on the structural and magnetic features of bidentate ligand-capped {CoII9[WV(CN)8]6} single-molecule magnets

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Supplementary files

Article information


Submitted
22 Oct 2015
Accepted
12 Jan 2016
First published
12 Jan 2016

CrystEngComm, 2016,18, 1495-1504
Article type
Paper
Author version available

The solvent effect on the structural and magnetic features of bidentate ligand-capped {CoII9[WV(CN)8]6} single-molecule magnets

S. Chorazy, A. Hoczek, M. Kubicki, H. Tokoro, S. Ohkoshi, B. Sieklucka and R. Podgajny, CrystEngComm, 2016, 18, 1495
DOI: 10.1039/C5CE02064F

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