Bifunctionalized Metal-Organic Frameworks for Pore-Size-Dependent Enantioselective Sensing

Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202204066. doi: 10.1002/anie.202204066. Epub 2022 Apr 21.

Abstract

Porosity is a fundamental property of metal-organic frameworks (MOFs). However, the role of the pore size has always been underestimated in MOF-based luminescent sensors for enantioselective sensing. The construction of isoreticular MOFs (IRMOFs) with variable pore sizes and the synergy between chirality and luminescence is challenging. Herein, a general strategy was developed to introduce chirality into two well-known IRMOF-74 analogs with nanochannels of identical shapes but different pore sizes by functionalizing the open metal site under mild conditions. To enhance the detection accuracy, a second luminescent center was introduced into the IRMOF-74 system to achieve ratiometric sensing. The two bifunctionalized IRMOF-74 compounds exhibited pore-size-dependent sensing performance for enantiomers. This study not only provides a convenient method to construct chiral MOFs as advanced sensing materials but also reveals the fundamental of the pores in MOF-based luminescent sensors.

Keywords: Enantioselective Sensing; Luminescent Sensor; Metal-Organic Frameworks; Pore-Size Dependence; Ratiometric Sensing.