Lanthanoid “Bottlebrush” Clusters: Remarkably Elongated Metal–Oxo Core Structures with Controllable Lengths

Large metal–oxo clusters consistently assume spherical or regular polyhedral morphologies rather than high-aspect-ratio structures. Access to elongated core structures has now been achieved by the reaction of lanthanoid salts with a tetrazole-functionalized calix­arene in the presence of a simple ca...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-10, Vol.136 (43), p.15122-15125
Main Authors: D’Alessio, Daniel, Sobolev, Alexandre N, Skelton, Brian W, Fuller, Rebecca O, Woodward, Robert C, Lengkeek, Nigel A, Fraser, Benjamin H, Massi, Massimiliano, Ogden, Mark I
Format: Article
Language:English
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Summary:Large metal–oxo clusters consistently assume spherical or regular polyhedral morphologies rather than high-aspect-ratio structures. Access to elongated core structures has now been achieved by the reaction of lanthanoid salts with a tetrazole-functionalized calix­arene in the presence of a simple carboxylate co-ligand. The resulting Ln19 and Ln12 clusters are constructed from apex-fused Ln5O6 trigonal bipyramids and are formed consistently under a range of reaction conditions and reagent ratios. Altering the carboxylate co-ligand structure reliably controls the cluster length, giving access to a new class of rod-like clusters of variable length.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja506677h