Self-assembled, hollow molecular structures are appealing as synthetic hosts for mediating chemical reactions. However, product binding has inhibited catalytic turnover in such systems, and selectivity has rarely approached the levels observed in more structurally elaborate natural enzymes. We found that an aqueous organopalladium cage induces highly unusual regioselectivity in the Diels-Alder coupling of anthracene and phthalimide guests, promoting reaction at a terminal rather than central anthracene ring. Moreover, a similar bowl-shaped host attains efficient catalytic turnover in coupling the same substrates (although with the conventional regiochemistry), most likely because the product geometry inhibits the aromatic stacking interactions that attract the planar reagents to the host.

Two Molecular Spheres: Viruses form highly symmetrical coat structures, capsids, through the assembly of multiple lower-symmetry protein precursors. Recently, chemists have sought to emulate this process on a smaller scale, relying on the assembly of organic molecular struts and metal ions, rather than proteins. Sun et al. (p. 1144 , published online 29 April; see the Perspective by Stefankiewicz and Sanders ) now demonstrate that a mixture of palladium ions and V-shaped bridging ligands can self-assemble into a hollow, nearly spherical polyhedron with 24 vertices and a central diameter of 4 nanometers. The assembly process was highly sensitive to the ligand angle; a subtle average decrease generated instead a smaller 12-vertex product.

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.