Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN− Apical Ligands

The selective preparation, structural and spectroscopic study of two new rhenium cluster complexes trans-[Re6S8(bpy)4(CN)2] and trans-[Re6S<sub&...

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Autores principales:	Anton A. Ulantikov, Taisiya S. Sukhikh, Evgeniy N. Gribov, Natalia V. Maltseva, Konstantin A. Brylev, Yuri V. Mironov, Yakov M. Gayfulin
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	rhenium cluster redox-active ligands crystal structure electronic structure Mathematics QA1-939
Acceso en línea:	https://doaj.org/article/cccfb440fa4d4f79a479108ab907155b
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spelling	oai:doaj.org-article:cccfb440fa4d4f79a479108ab907155b2021-11-25T19:07:26ZThermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands10.3390/sym131121872073-8994https://doaj.org/article/cccfb440fa4d4f79a479108ab907155b2021-11-01T00:00:00Zhttps://www.mdpi.com/2073-8994/13/11/2187https://doaj.org/toc/2073-8994The 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.Anton A. UlantikovTaisiya S. SukhikhEvgeniy N. GribovNatalia V. MaltsevaKonstantin A. BrylevYuri V. MironovYakov M. GayfulinMDPI AGarticlerhenium clusterredox-active ligandscrystal structureelectronic structureMathematicsQA1-939ENSymmetry, Vol 13, Iss 2187, p 2187 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	rhenium cluster redox-active ligands crystal structure electronic structure Mathematics QA1-939
spellingShingle	rhenium cluster redox-active ligands crystal structure electronic structure Mathematics QA1-939 Anton A. Ulantikov Taisiya S. Sukhikh Evgeniy N. Gribov Natalia V. Maltseva Konstantin A. Brylev Yuri V. Mironov Yakov M. Gayfulin Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands
description	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.
format	article
author	Anton A. Ulantikov Taisiya S. Sukhikh Evgeniy N. Gribov Natalia V. Maltseva Konstantin A. Brylev Yuri V. Mironov Yakov M. Gayfulin
author_facet	Anton A. Ulantikov Taisiya S. Sukhikh Evgeniy N. Gribov Natalia V. Maltseva Konstantin A. Brylev Yuri V. Mironov Yakov M. Gayfulin
author_sort	Anton A. Ulantikov
title	Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands
title_short	Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands
title_full	Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands
title_fullStr	Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands
title_full_unstemmed	Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands
title_sort	thermally controlled synthesis of octahedral rhenium clusters with 4,4′-bipyridine and cn<sup>−</sup> apical ligands
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/cccfb440fa4d4f79a479108ab907155b
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Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN<sup>−</sup> Apical Ligands

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