Self-assembly of polyhedral metal–organic framework particles into three-dimensional ordered superstructures

Self-assembly of particles into long-range, three-dimensional, ordered superstructures is crucial for the design of a variety of materials, including plasmonic sensing materials, energy or gas storage systems, catalysts and photonic crystals. Here, we have combined experimental and simulation data to show that truncated rhombic dodecahedral particles of the metal–organic framework (MOF) ZIF-8 can self-assemble into millimetre-sized superstructures with an underlying three-dimensional rhombohedral lattice that behave as photonic crystals. Those superstructures feature a photonic bandgap that can be tuned by controlling the size of the ZIF-8 particles and is also responsive to the adsorption of guest substances in the micropores of the ZIF-8 particles. In addition, superstructures with different lattices can also be assembled by tuning the truncation of ZIF-8 particles, or by using octahedral UiO-66 MOF particles instead. These well-ordered, sub-micrometre-sized superstructures might ultimately facilitate the design of three-dimensional photonic materials for applications in sensing.