Journal of the American Chemical Society, Vol.136, No.43, 15122-15125, 2014
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 carboxylate co-ligand. The resulting Ln(19) and Ln(12) clusters are constructed from apex-fused Ln(5)O(6) 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.