NDLI: Spontaneous Resolution of Chiral Polyoxometalate-Based Compounds Consisting of 3D Chiral Inorganic Skeletons Assembled from Different Helical Units

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Spontaneous Resolution of Chiral Polyoxometalate-Based Compounds Consisting of 3D Chiral Inorganic Skeletons Assembled from Different Helical Units

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Wang, Xin-long Du, Dong-ying Wang, En-bo Su, Zhong-min Lan, Ya-qian Li, Shun-li Shao, Kui-zhan
Description	Author Affiliation: Lan YQ ( Institute of Functional Material Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, People's Republic of China.)
Abstract	Four enantiomerically pure 3D chiral POM-based compounds, $[Ni_{2}(bbi)_{2}(H_{2}O)_{4}V_{4}O_{12}]⋅2 H_{2}O$ (1 a and 1 b) and $[Co(bbi)(H_{2}O)V_{2}O_{6}]$ (2 a and 2 b) (bbi=1,1′-(1,4-butanediyl)bisimidazole) based on the achiral ligand, different vanadate chains, and different metal centers have been synthesized by hydrothermal methods. Single-crystal X-ray diffraction analyses revealed that 1 a and 1 b, and 2 a and 2 b, respectively, are enantiomers. In 1 a and 1 b two kinds of vanadate chains with different screw axes link Ni cations to generate 3D chiral inorganic skeletons, which are connected by the achiral bbi ligands to form complicated 3D 3,4-connected chiral self-penetrating frameworks with $(7^{2}⋅8)(7^{2}⋅8^{2}⋅9^{2})(7^{3}⋅8^{2}⋅10)$ topology. They represent the first examples of chiral self-penetrating frameworks known for polyoxometalate (POM) systems. Contrary to 1 a and 1 b, in 2 a and 2 b the vanadate chains link $Co^{II}$ cations to generate 3D chiral inorganic skeletons, which are assembled from two kinds of heterometallic helical units of opposite chirality along the c axes. The chiral inorganic skeletons are connected by bbi to form 3D 3,4-connected chiral POM-based frameworks with $(6^{2}⋅8)_{2}(6^{2}⋅8^{2}⋅10^{2})$ topology. It is believed that the asymmetrical coordination modes of the metal cations in 1 a–2 b generate the initial chiral centers, and that the formation of the various helical units and the hydrogen bond interactions are responsible for preservation of the chirality and spontaneous resolution when the chirality is extended into the homochiral 3D-networks. This is the first known report of chiral POM-based compounds consisting of 3D chiral inorganic skeletons being obtained by spontaneous resolution upon crystallization in the absence of any chiral source, which may provide a rational strategy for synthesis of chiral POM-based compounds by using achiral ligands and POM helical units.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	32
Volume Number	14
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2008-01-01
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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