Turning on Asymmetric Catalysis of Achiral Metal‐Organic Frameworks by Imparting Chiral Microenvironment

Abstract

The development of heterogeneous asymmetric catalysts has attracted increasing interest in synthetic chemistry but mostly relies on the immobilization of homogeneous chiral catalysts. Herein, a series of chiral metal‐organic frameworks (MOFs) have been fabricated by anchoring similar chiral hydroxylated molecules (catalytically inactive) with different lengths onto Zr‐oxo clusters in achiral PCN‐222(Cu). The resulting chiral MOFs exhibit regulated enantioselectivity up to 83% ee in the asymmetric ring‐opening of cyclohexene oxide. The chiral molecules furnished onto the catalytic Lewis sites in the MOF create multilevel microenvironment, including the hydrogen interaction between the substrate and the chiral ‐OH group, the steric hindrance endowed by the benzene ring on the chiral molecules, and the proximity between the catalytic sites and chiral molecules confined in the MOF pores, which play crucial roles and synergistically promote chiral catalysis. This work unprecedentedly achieves heterogeneous enantioselective catalysis by chiral microenvironment modulation around Lewis acid sites.

Boosting structural variety and catalytic activity of porphyrinic metal–organic frameworks by harnessing bifunctional ligands

“…Additionally, PMOFs can provide large surface areas and pore volumes, high tunable architecture, and confined spaces for catalytic reactions, which are beneficial for improving their catalytic selectivity and activity. 25,26 Moreover, the precise structures make PMOFs a preferred platform to study the relationship between structures and their catalytic performances.…”

Chiral ZnO-CuO Nanorod Arrays for Circularly Polarized Photodetection

“…It describes a geometric characteristic for which an object cannot be coincident with its image by simple rotation and translation . Materials with chiral structures have been widely used in various fields, e.g., identification and detection of enantiomers, catalysis, information encryption, and optical communication . Common photodetectors made of achiral semiconductors are unable to detect CPL (circularly polarized light) directly.…”

Ratiometric Electrochemiluminescence of Zirconium Metal–Organic Framework as a Single Luminophore for Sensitive Detection of HPV-16 DNA

“…The metal–organic framework (MOF) is a type of crystalline material which is composed of central metal ions or clusters and bridged organic ligands. − Due to its excellent performance of designable and tunable function, the MOF material has strong application outlooks in the electrochemical biosensor domain, particularly in terms of the MOF as the ECL luminophore. − More impressively, some dual-ligand MOF materials with better performance have been developed that combine different functional ligands to achieve dual functionalization. For instance, Zhang’s group prepared the M6-MOF with two links of 1,3,6,8-tetra (4′-carboxyphenyl) pyrene (TABPy) and 5,10,15,20-tetra­(4-carboxyphenyl)­porphyrin (TCPP), where TCPP facilitated electron transfer to enhance the ECL emission of TABPy .…”