Spontaneous Self-Assembly of Metal−Organic Cationic Nanocages to Form Monodisperse Hollow Vesicles in Dilute Solutions

In this communication we report the unprecedented spontaneous self-assembly of cationic nanoporous metal-organic coordination cages (nanocages) into giant hollow vesicle-like structures in polar solvents. Such highly soluble nanocages (macrocations) have separated hydrophobic regions. However, their assembly is not due to hydrophobic interactions but the counterion-mediated attractions, very similar to the unique self-assembly of polyoxometalate macroanions into single-layer, spherical blackberry structures, as characterized by laser light scattering and TEM studies. This is the first study on the solution behavior of metal-organic nanocages and also the first report on the self-assembly of soluble macrocations. Therefore, the blackberry structure is likely to be a universal type of self-assembly for soluble macroions. In addition, the self-assembled nanocages can provide blackberry structures a wide range of organic functionalities that are impossible to reach with purely inorganic systems, which may open the door to many types of applications.