Chiral and robust Zr(IV)-based metal-organic frameworks built from spiro skeletons.

Chiral metal-organic frameworks (CMOFs) have emerged as an important subclass of chiral materials; however, their development is hindered substantially by limited enantiopure functional linkers and poor chemical stabilities. Here we report the design and synthesis of a total of five enantiopure spiro-based tetracarboxylate linkers with diverse functionalities and their use in connecting Zr6 clusters to form an array of highly robust and porous CMOFs. X-ray crystallographic analysis and structure examination unambiguously revealed that the resulting CMOFs possess multifarious three-dimensional networks with novel topologies and pore systems, highlighting the great potential of chiral spiro skeletons in the fabrication of intriguing structures. PXRD and N2 adsorption experiments validated their exceptional chemical stability towards boiling water as well as aqueous acid and base solutions. Moreover, their potential applications in enantioselective catalysis and separation are also presented.