One‐Step Room‐Temperature Synthesis of Metal(IV) Carboxylate Metal—Organic Frameworks

Room‐temperature syntheses of metal–organic frameworks (MOFs) are of interest to meet the demand of the sustainable chemistry and are a pre‐requisite for the incorporation of functional compounds in water‐stable MOFs. However, only few routes under ambient conditions have been reported to produce metal(IV)‐based MOFs. Reported here is a new versatile one‐step synthesis of a series of highly porous M6‐oxocluster‐based MOFs (M=Zr, Hf, Ce) at room temperature, including 8‐ or 12‐connected micro/mesoporous solids with different functionalized organic ligands. The compounds show varying degrees of defects, particularly for 12‐connected phases, while maintaining the chemical stability of the parent MOFs. Proposed here are first insights into in situ kinetics observations for efficient MOF preparation. Remarkably, the synthesis has a high space‐time yield and also provides the possibility to tune the particle size, therefore paving the way for their practical use. Several micro/mesoporous metal(IV)‐based metal—organic frameworks (MOFs) with different functional groups were synthesized at room temperature using environmentally friendly conditions. The versatility of this strategy allows use of different reactants, and control of the MOF particle size. A synthesis using a pilot scale‐up system demonstrates the potential of this approach for the industrial production of metal(IV)‐based MOFs.