From Platonic Templates to Archimedean Solids: Successive Construction of Nanoscopic {V16As8}, {V16As10}, {V20As8}, and {V24As8} Polyoxovanadate Cages
- 30 June 2011
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 133 (29), 11240-11248
- https://doi.org/10.1021/ja2024004
Abstract
Supramolecular coordination cages provide unique restricted inner cavities that can be exploited for molecular recognition purposes and catalysis. Their syntheses often involve complex self-organization processes and rely on the identification of preorganized, kinetically stable building units that provide ligand-accessible coordination sites. Here we report a highly effective protocol for the successive buildup of symmetrical nanoscopic polyoxometalate (POM) cages. Our methodology takes advantage of a supramolecular templating effect and utilizes the structure-directing influence of octahedral {X(x)(H(2)O)(6-x)} (X = Br(-), Cl(-); x = 2, 4, 6) assemblies that reside inside the hollow cluster shells and determine the arrangement of di- and tetranuclear vanadate units. The approach allows the preparation of a series of high-nuclearity POM cages that are characterized by {V(16)As(8)}, {V(16)As(10)}, {V(20)As(8)}, and {V(24)As(8)} core structures. In the latter cluster cage, the vanadium centers adopt a truncated octahedral topology. The formation of this Archimedean body is the direct result of the assembly of six square {V(4)O(8)} units that cap the vertices of the encapsulated Platonic {Cl(6)} octahedron. To the best of our knowledge, this {V(24)As(8)} cage is the largest hybrid vanadate cluster reported to date.Keywords
This publication has 57 references indexed in Scilit:
- Networked molecular cages as crystalline sponges for fullerenes and other guestsNature Chemistry, 2010
- Self-Assembled M 24 L 48 Polyhedra and Their Sharp Structural Switch upon Subtle Ligand VariationScience, 2010
- Keeping the Ball Rolling: Fullerene-like Molecular ClustersAccounts of Chemical Research, 2009
- Proton-Mediated Chemistry and Catalysis in a Self-Assembled Supramolecular HostAccounts of Chemical Research, 2009
- White Phosphorus Is Air-Stable Within a Self-Assembled Tetrahedral CapsuleScience, 2009
- Reticular Chemistry of Metal–Organic PolyhedraAngewandte Chemie-International Edition, 2008
- A Keplerate Magnetic Cluster Featuring an Icosidodecahedron of Ni(II) Ions Encapsulating a Dodecahedron of La(III) IonsJournal of the American Chemical Society, 2007
- Selective Molecular Recognition, C−H Bond Activation, and Catalysis in Nanoscale Reaction VesselsAccounts of Chemical Research, 2004
- High-Symmetry Coordination Cages via Self-AssemblyAccounts of Chemical Research, 2002
- Self-assembly of nanoscale cuboctahedra by coordination chemistryNature, 1999