Geometric curvature controls the chemical patchiness and self-assembly of nanoparticles

When organic molecules are tethered onto non-spherical nanoparticles, their chemical properties depend on the particles' local curvature and shape. Based on this observation, we show here that it is possible to engineer chemical patchiness across the surface of a non-spherical nanoparticle using a single chemical species. In particular, when acidic ligands are used, regions of the particle surface with different curvature become charged at different pH values of the surrounding solution. This interplay between particle shape and local electrostatics allows for fine control over nanoscale self-assembly leading to structures with varying degrees of complexity. These structures range from particle cross-stacks to open-lattice crystals, the latter with pore sizes on the order of tens of nanometres, that is, at the lower synthetic limits of metallic mesoporous materials.