Up–down approach for expanding the chemical space of metal–organic frameworks

Abstract Metal-organic frameworks (MOFs) have become materials platform with vast structural diversity, tailorable for broad practical applications. Traditional bottom-up and top-down design approaches played a pivotal role for a rapid increase in MOF structures, yet the systematic screening for unknown synthesizable MOFs is still a daunting challenge. Herein, we developed a novel search paradigm, the Up-Down Approach (UDA), by merging the bottom-up and top-down approaches. Targeting the famous class of Zr-based MOFs, we searched promising topology candidates and unveiled 17 future structural configurations by considering the possible orientations of Zr6 clusters. Through ribbon representation and sophisticated analysis of the ligand angles, we suggested future structure models and successfully synthesized one of the suggested structures with a novel scu configuration. The UDA will accelerate the discovery of hidden MOFs, providing exciting new opportunities to effectively expand the chemical space of MOFs.