Role of Prenucleation Building Units in Determining Metal–Organic Framework MIL-53(Al) Morphology

While it is well-known that the particle size of solvothermally synthesized metal–organic frameworks (MOFs) can be controlled by tuning the solvent composition, which affects the solubility of the linker and metal salt educts, the exact relationship between linker solubility, initial chemical coordination steps occurring in solution, and the resulting MOFs’ particle size has not yet been investigated. Here, we have studied the solvothermal synthesis of MIL-53(Al) in DMF and water/DMF mixtures with in situ Raman spectroscopy, which reveals the formation of intermediate prenucleation building unit (PNBU) species that consist of one linker molecule and one metal atom and self-assemble in solution to form MIL-53(Al). The concentration of PNBUs in solution prior to particle precipitation is dependent on the synthesis solvent ratio used and influences the MIL-53 particle size. Synthesis in pure DMF results in a high concentration of PNBUs in solution prior to MOF supersaturation and precipitation. This results in a large burst of MOF nucleation and the formation of nanosized MIL-53(Al) particles. Adding water to the DMF solution leads to reduced PNBU accumulation in solution prior to MOF precipitation due to the reduced linker solubility. The reduced accumulation of PNBUs prior to particle precipitation causes reduced nucleation and favors particle growth. The MIL-53(Al) particle size, in contrast, is independent of the MOF phase growth rate, which is highly dependent on the synthesis temperature.