Co-Crystals of Atomically Precise Nanoclusters with Organic Macrocycles

Atomically precise nanoclusters combine the unique, size-depended properties of nanoparticles with the structural and chemical uniformity of molecules, making them powerful building blocks for the synthesis of functional nanomaterials. Here, we discuss a strategy to assemble nanoclusters into solid-state materials with tunable structures and properties by leveraging supramolecular interactions mediated by charged organic macrocycles. The high level of structural control afforded by the resulting nanocluster-organic ionic cocrystals allows cluster packing and the orientation of cluster surface ligands to be controlled through the judicious design of macrocycles with specifically tailored size, symmetry, and ionic charge. When the organic macrocycle is appropriately matched to the nanocluster, for example, this enables chirogenesis—the emergence of chirality from an achiral organic molecule and an achiral inorganic nanocluster—and leads to large solid-state chiroptical effects. Broadly, we will describe how our approach could provide access to a new phase space of highly tunable atomically precise nanomaterials with unique properties and functions.