Giant hollow MnL2n spherical complexes: structure, functionalisation and applications

Abstract

Drawing inspiration from the self-assembly of hollow spherical virus capsids and protein cages found in nature, a family of roughly spherical coordination polyhedra with general formula M_nL_2n was designed and several members of the series have been synthesised. These spherical complexes are self-assembled upon reaction of bent bis(pyridine) ligands with Pd²⁺ ions. The introduction of functional side chains into the ligands is straightforward, making the synthesis of both exo- and endohedrally functionalised spherical complexes possible. Accumulation of a high density of functional groups at the periphery of the spherical framework results in an enhancement of the weak interactions used in biomolecular recognition processes and the strong and selective interaction of the complex with a variety of substrates. Discrete and well-defined environments are generated within the spherical framework by functionalisation of the interior of the complex. These environments can be used for the selective encapsulation of guest molecules, including species as diverse as simple metal ions, fluoroalkanes and fullerenes. The well-defined cavity of the spherical complexes can also be exploited for the synthesis of precisely size-controlled nanoparticles and polymers. Most recently, a protein was successfully enclosed within a hollow self-assembled spherical complex, with a long-term view towards the control of protein functions for the development of new applications.