PolyMOF Nanoparticles: Dual Roles of a Multivalent polyMOF Ligand in Size Control and Surface Functionalization

Metal-organic framework nanoparticles (MOF NPs) have emerged as an important class of materials that display significantly enhanced performance in many applications compared to bulk MOF materials; their synthesis, however, commonly involves a tedious sequence that controls particle size and surface properties in separate steps. Now, a simple strategy to access functional MOF NPs in one pot is reported that uses a polyMOF ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF-5 NPs with sizes down to 20 nm, displaying exceptional structural and colloidal stability upon exposure to ambient conditions. A detailed time-dependent study revealed that the polyMOF NPs were formed following an aggregation-confined crystallization mechanism. Generality was demonstrated through the synthesis of well-defined polyUiO-66 NPs.