A robust Zr-MOF (LIFM-28) containing replaceable coordination sites for additional spacer installation has been employed to demonstrate a swing- or multirole strategy for multifunctional MOFs. Through reversible installation/uninstallation of two types of spacers with different lengths and variable functional groups, different tasks can be accomplished using the same parent MOF. An orthogonal optimizing method is applied with seven shorter (L) and six longer (L) spacers to tune the functionalities, achieving multipurpose switches among gas separation, catalysis, click reaction, luminescence, and particularly, ultrahigh methane storage working capacity at 5-80 bar and 298 K.

The stereochemistry of chiral-at-metal complexes is much more abundant, albeit complicated, than chiral-at-carbon compounds, but how to make use of stereolabile metal-centers remains a formidable challenge due to the highly versatile coordination geometry of metal ions and racemization/epimerization problem. We demonstrate herein a stepwise assembly of configurationally stable [Pd 6 (FeL 3 ) 8 ] 28+ (Δ/Λ-MOCs-42) homochiral octahedral cages from unstable D 3 -symmetry trischelate-Fe type metalloligands via strong face-directed stereochemical coupling and facile chiral-induced resolution processes based on stereodifferentiating host−guest dynamics. Kinetic studies reveal that the dissociation rate of MOC-42 cages is 100-fold slower than that of Femetalloligands and the racemization is effectively inhibited, making the cages retain their chirality over extended periods of time (>5 months) at room temperature. Recyclable enantioseparation of atropisomeric compounds has been successfully achieved, giving up to 88% ee.

Development of chiral ligands is the most fundamental task in metal-catalyzed asymmetric synthesis. In the last 60 years, various kinds of ligands have been sophisticatedly developed. However, it remains a long-standing challenge to develop practically useful chiral η 6 -arene ligands, thereby seriously hampering the asymmetric synthesis promoted by arene-metal catalysts. Herein, we report the design and synthesis of a class of readily tunable, C 2 -symmetric chiral arene ligands derived from [2.2]paracyclophane. Its ruthenium(II) complexes have been prepared and successfully applied in the enantioselective CÀ H activation to afford a series of axially chiral isoquinolones (up to 99 % yield and 96 % ee). This study not only lays chemists' longstanding doubts about whether it is possible to use chiral arene ligands to stereocontrol ruthenium(II)-catalyzed asymmetric CÀ H activation, but also opens up a new avenue to achieve asymmetric CÀ H activation.

Direct white-light emission was first achieved in a single phase material of a Dy(III) metal-organic framework, which also shows tunable yellow-to-blue photoluminescence upon variation of excitation wavelengths.