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

Angew Chem Int Ed Engl. 2021 Feb 19;60(8):4282-4288. doi: 10.1002/anie.202014184. Epub 2020 Dec 23.

Abstract

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.

Keywords: mesoporous materials; metal-organic frameworks; microporous materials; synthetic methods.