The effective synthesis of chiral compounds in a highly enantioselective manner is obviously attractive. Inspired by the enzymatic reactions that occur in pocket‐like cavities with high efficiency and specificity, chemists are seeking to construct catalysts that mimic this key feature of enzymes. Recent progress in supramolecular coordination chemistry has shown that metal–organic cages (MOCs) and metal–organic frameworks (MOFs) with chiral confined cavities/pores may offer a novel platform for achieving asymmetric catalysis with high enantioselectivity. The inherent chiral confined microenvironment is considered to be analogous to the binding pocket of enzymes, and this pocket promotes enantioselective transformations. This work focuses on the recent advances in MOCs and MOFs with chiral confined spaces for asymmetric catalysis, and each section is separated into two parts based on how the chirality is achieved in these metal–organic architectures. A special emphasis is placed on discussing the relationship between the enantioselectivity and the confined spaces of the chiral functional MOCs and MOFs rather than catalytic chemistry. Finally, current challenges and perspectives are discussed. This work is anticipated to offer researchers insights into the design of sophisticated chiral confined space‐based metal–organic architectures for asymmetric catalysis with high enantioselectivity.

The development of DNA‐targeted photodynamic therapy (PDT) agents for cancer treatment has drawn substantial attention. Herein, the design and synthesis of dinuclear IrIII‐containing luminescent metallohelices with tunable PDT efficacy that target mitochondrial DNA in cancer cells are reported. The metallohelices are fabricated using dynamic imine‐coupling chemistry between aldehyde end‐capped fac‐Ir(ppy)3 handles and linear alkanediamine spacers, followed by reduction of the imine linkages. The length and odd–even character of the diamine alkyl linker determined the stereochemistry (helicates vs. mesocates). Compared to the helicates, the mesocates exhibit improved apoptosis‐induction upon white‐light irradiation. Molecular docking studies indicate that the mesocate with a proper length of diamine spacers shows stronger affinity for the minor groove of DNA. This study highlights the potential of DNA‐targeting IrIII‐containing metallohelices as PDT agents.

By introducing photoactive fac-tris(2-phenylpyridine)iridium moieties as a ligand backbone to constrain the coordination geometry of cobalt ions, a multifunctional Ir2Co3-type capsule was achieved and showed induced-fit capsule-capsule conversion by cooperative binding one carbonate anion with the equatorial Co(ii) centers. The capsule combined photocatalysis and transition metal activation synergistically and exhibited efficient catalytic ability on visible light-activated α-trichloromethylation.