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Rational Syntheses of Three New {V14Sb8} Clusters Applying a Water-Soluble High-Nuclearity Cluster as Synthon

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posted on 2018-08-20, 00:00 authored by Lisa K. Mahnke, Michael Wendt, Christian Näther, Wolfgang Bensch
We report the rational solvothermal syntheses and crystal structures of three new antimonato-polyoxovanadates, {Zn­(phen)3}2­[V14­Sb8O42­(H2O)]·0.5 phen·17 H2O (1), [{Zn­(en)2}2­V14­Sb8O42]·7 H2O (2), and {Fe­(phen)3}2­[V14­Sb8O42­(H2O)]·11 H2O (3), using the water-soluble {Zn­(en)3}3­[V15­Sb6O42­(H2O)]·3en·10H2O as synthon. The solvothermal reactions are fast and product formation is finished within 24 h. Adjustment of the pH value by application of an ammonia buffer avoided crystallization of the {V15Sb6­O42} core containing products. In the structure of 1, the en ligands of the starting compound are in situ exchanged by phen molecules. In 2, one en ligand of the [Zn­(en)3]2+ complexes of the educt is emitted under the reaction conditions, leading to crystallization of a layered structure formed by V–O–​Zn–​O bonds. Finally, in compound 3, the initially Zn2+-centered complexes are exchanged in situ by Fe2+-centered complexes with phen ligands. In all three structures, short intercluster Sb···O separations indicate weak interactions, leading to aggregates of higher dimensionality. The crystal water molecules are connected by intermolecular hydrogen bonds, leading to the formation of different types of water clusters. In addition, the water molecules are involved in hydrogen bonding to the cluster anions and ligands of the transition metal complexes.

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