Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands
The selective preparation, structural and spectroscopic study of two new rhenium cluster complexes <i>trans</i>-[Re<sub>6</sub>S<sub>8</sub>(bpy)<sub>4</sub>(CN)<sub>2</sub>] and <i>trans</i>-[Re<sub>6</sub>S<sub&...
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| Autores principales: | , , , , , , |
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| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
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| Materias: | |
| Acceso en línea: | https://doaj.org/article/cccfb440fa4d4f79a479108ab907155b |
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| Sumario: | The selective preparation, structural and spectroscopic study of two new rhenium cluster complexes <i>trans</i>-[Re<sub>6</sub>S<sub>8</sub>(bpy)<sub>4</sub>(CN)<sub>2</sub>] and <i>trans</i>-[Re<sub>6</sub>S<sub>8</sub>(bpy)<sub>2</sub>(CN)<sub>4</sub>]<sup>2−</sup> (bpy = 4,4′-bipyridine) obtained by reactions of corresponding hexarhenium cyanohalides with molten bpy are reported. The complexes were crystallized as solvates, displaying supramolecular structures based on cluster units linked by numerous weak interactions with bpy molecules. The molecular compound <i>trans</i>-[Re<sub>6</sub>S<sub>8</sub>(bpy)<sub>4</sub>(CN)<sub>2</sub>] (<b>1</b>) is insoluble in water and common organic solvents, while the ionic compound <i>trans</i>-Cs<sub>1.7</sub>K<sub>0.3</sub>[Re<sub>6</sub>S<sub>8</sub>(bpy)<sub>2</sub>(CN)<sub>4</sub>] (<b>2</b>) is somewhat soluble in DMSO, DMF and N-methylpyrrolidone. The presence of the redox-active ligand bpy leads to the occurrence of multi-electron reduction transitions in a solution of <b>2</b> at moderate potential values. The ambidentate CN<sup>−</sup> ligand is the secondary functional group, which has potential for the synthesis of coordination polymers based on the new cluster complexes. In addition, both new compounds show a weak red luminescence, which is characteristic of complexes with a {Re<sub>6</sub>S<sub>8</sub>}<sup>2+</sup> cluster core. |
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