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Systematic construction of progressively larger metal-organic cages from a 5-fold linking subcomponent
K. Wu, T.K. Ronson, P. Su, Z. Chen, A.W. Heard, X. Li, F. Klautzsch, C.A. Schalley, M. Vinkovic, J.R. Nitschke – 2023
Biological encapsulants, such as viral capsids and ferritin protein cages, use many identical subunits to tile the surface of a polyhedron. Inspired by these natural systems, synthetic chemists have prepared an extensive series of artificial nanocages, with well-defined shapes and cavities. Rational control over the self-assembly of discrete, large, hollow coordination nanocages composed of simple components still poses great challenges as a result of the entropic costs associated with binding many subunits together, difficulties in the error-correction processes associated with assembly, and increasing surface energy as their size grows. Here we demonstrate the construction of a family of nanocages of increasing size derived from a single simple pentatopic pyrrole-based subcomponent. Reasoned shifts in the preferred coordination number of the metal ions employed, along with the denticity and steric hindrance of the ligands, enabled the generation of progressively larger cages, incorporating more subunits. These ‘mutations’ are reminiscent of minor variations in the amino acid sequences of proteins; understanding how they impact capsule structure and thus cavity size may help to elucidate construction principles for still larger, more complex and functional capsules, capable of binding and carrying large biomolecules as cargoes.
Systematic construction of progressively larger metal-organic cages from a 5-fold linking subcomponent