Discrete Supracrystalline Heterostructures from Integrative Assembly of Nanocrystals and Porous Organic Cages.

Although self-assembly across multiple length scales has been well recognized and intensively investigated in natural biological system, the design of artificial heterostructures enabled by integrative self-assembly is still in its infancy. Here we report a strategy toward the growth of discrete supracrystalline heterostructures from inorganic nanocrystals and porous organic cages (), which in principle relies on the host-guest interactions between alkyl chains coated on nanocrystals and the cavity of cage molecules. Density functional theory calculation indicates that an attractive energy of ∼-2 T is present between an alkyl chain and the cavity of a molecule, which is responsible for the assembly of nanocrystal superlattices on the octahedral crystals. Of particular interest is that, determined by the shape of the nanocrystals, two distinct assembly modes can be controlled at the mesoscale level, which eventually produce either a core/shell or heterodimer supracrystalline structure. Our results highlight opportunities for the development of such a noncovalent integrative self-assembly not limited to a particular length scale and that could be generally applicable for flexible integration of supramolecular systems.