Integrative self-sorting of coordination cages based on ‘naked’ metal ions
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Date
2017-08-07
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Abstract
Coordination-driven self-assembly of metal ions and organic ligands has been extensively utilised over
the past four decades to access a variety of nano-sized cage assemblies, with functions ranging from
sensing and catalysis to drug delivery. Many of the reported examples, however, are highly symmetric
architectures that contain one type of organic ligand carrying not more than a single functionality. This
contrasts significantly with the level of structural and functional complexity encountered in biological
macromolecular hosts, which are able to bind and chemically convert smaller molecules in their highly-
decorated internal cavities. To address this disparity, rational approaches that facilitate heteroleptic
assembly by regulating integrative self-sorting of metal ions and multiple ligand components have
emerged. Among these, routes to access coordination cages from ‘naked’ metal cations that offer more
than two coordination sites are still in early development, as the complexity of the self-sorted products
in terms of composition and stereochemistry presents an entropic challenge. This feature article
highlights recent progress in controlling integrative self-sorting of multi-component cage systems with a
focus on structures composed of ‘naked’ metal cations and two different ligands. Once heteroleptic
self-assembly strategies find a wider implementation in supramolecular design, the resultant interplay
between tailored combinations of precisely positioned substituents promises enhanced functionality in
nanoscale structures.
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Keywords
Integrative self-sorting, Heteroleptic self assembly, Multicomponent cage system, Supramolecular chemistry