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Afterglow materials have garnered significant interest due to distinct photophysical characteristics. However, it is still difficult to achieve long afterglow phosphorescence from organic molecules due to aggregation-caused quenching (ACQ) and energy dissipation. In addition, most materials reported so far have long afterglow emission only at room or even low temperatures, and mainly use UV light as an excitation source. In this work, we report a strategy to achieve high temperature long afterglow emission through the assembly of isolated 0D metal-organic cages (MOCs). In which, both ACQ and phosphorescence quenching effects are effectively mitigated by altering the stacking mode of organic chromophores through orthogonally anchoring into the edges of cubic MOCs. Furthermore, improvement in molecular rigidity, promotion of spin-orbit coupling and broadening of the absorption range are achieved through the MOC-engineering strategy. As a result, we successfully synthesized MOCs that can produce afterglow emission even after excitation by WLEDs at high temperatures (380 K). Moreover, the MOCs are capable of generating afterglow emissions when excited by mobile phone flashlight at room temperature. Given these features, the potential applications of MOCs in the visual identification of explosives, information encryption and multicolor display are explored., (© 2024 Wiley-VCH GmbH.)

Achieving high guest loading and multiguest-binding capacity holds crucial significance for advancement in separation, catalysis, and drug delivery with synthetic receptors; however, it remains a challenging bottleneck in characterization of high-stoichiometry guest-binding events. Herein, we describe a large-sized coordination cage (MOC-70-Zn 8 Pd 6 ) possessing 12 peripheral pockets capable of accommodating multiple guests and a high-resolution electrospray ionization mass spectrometry (HR-ESI-MS)-based method to understand the solution host-guest chemistry. A diverse range of bulky guests, varying from drug molecules to rigid fullerenes as well as flexible host molecules of crown ethers and calixarenes, could be loaded into open pockets with high capacities. Notably, these hollow cage pockets provide multisites to capture different guests, showing heteroguest coloading behavior to capture binary, ternary, or even quaternary guests. Moreover, a pair of commercially applied drugs for the combination therapy of chronic lymphocytic leukemia (CLL) has been tested, highlighting its potential in multidrug delivery for combined treatment.

The structural dynamics of artificial assemblies, in aspects such as molecular recognition and structural transformation, provide us with a blueprint to achieve bioinspired applications. Here, we describe the assembly of redox-switchable chiral metal-organic cages Λ 8 /Δ 8 -[Pd 6 (Co II L 3 ) 8 ] 28+ and Λ 8 /Δ 8 -[Pd 6 (Co III L 3 ) 8 ] 36+ . These isomeric cages demonstrate an on-off chirality logic gate controlled by their chemical and stereostructural dynamics tunable through redox transitions between the labile Co II -state and static Co III -state with a distinct Cotton effect. The transition between different states is enabled by a reversible redox process and chiral recognition originating in the tris-chelate Co-centers. All cages in two states are thoroughly characterized by NMR, ESI-MS, CV, CD, and X-ray crystallographic analysis, which clarify their redox-switching behaviors upon chemical reduction/oxidation. The stereochemical lability of the Co II -center endows the Λ 8 /Δ 8 -Co II -cages with efficient chiral-induction by enantiomeric guests, leading to enantiomeric isomerization to switch between Λ 8 /Δ 8 -Co II -cages, which can be stabilized by oxidation to their chemically inert forms of Λ 8 /Δ 8 -Co III -cages. Kinetic studies reveal that the isomerization rate of the Δ 8 -Co III -cage is at least an order of magnitude slower than that of the Δ 8 -Co II -cage even at an elevated temperature, while its activation energy is 16 kcal mol -1 higher than that of the Co II -cage.

A series of isostructural supramolecular cages with a rhombic dodecahedron shape have been assembled with distinct metal-coordination lability (M 8 Pd 6 -MOC-16, M=Ru 2+ , Fe 2+ , Ni 2+ , Zn 2+ ). The chirality transfer between metal centers generally imposes homochirality on individual cages to enable solvent-dependent spontaneous resolution of Δ 8 /Λ 8 -M 8 Pd 6 enantiomers; however, their distinguishable stereochemical dynamics manifests differential chiral phenomena governed by the cage stability following the order Ru 8 Pd 6 >Ni 8 Pd 6 >Fe 8 Pd 6 >Zn 8 Pd 6 . The highly labile Zn centers endow the Zn 8 Pd 6 cage with conformational flexibility and deformation, enabling intrigue chiral-Δ 8 /Λ 8 -Zn 8 Pd 6 to meso-Δ 4 Λ 4 -Zn 8 Pd 6 transition induced by anions. The cage stabilization effect differs from inert Ru 2+ , metastable Fe 2+ /Ni 2+ , and labile Zn 2+ , resulting in different chiral-guest induction. Strikingly, solvent-mediated host-guest interactions have been revealed for Δ 8 /Λ 8 -(Ru/Ni/Fe) 8 Pd 6 cages to discriminate the chiral recognition of the guests with opposite chirality. These results demonstrate a versatile procedure to control the stereochemistry of metal-organic cages based on the dynamic metal centers, thus providing guidance to maneuver cage chirality at a supramolecular level by virtue of the solvent, anion, and guest to benefit practical applications., (© 2023 Wiley-VCH GmbH.)

Molecular recognition lies at the heart of biological functions, which inspires lasting research in artificial host syntheses to mimic biomolecules that can recognize, process, and transport molecules with the highest level of complexity; nonetheless, the design principle and quantifying methodology of artificial hosts for multiple guests (≥4) remain a formidable task. Herein, we report two rhombic dodecahedral cages [(Zn/Fe) 8 Pd 6 -MOC-16], which embrace 12 adaptive pockets for multiguest binding with distinct conformational dynamics inherent in metal-center lability and are able to capture 4-24 guests to manifest a surprising complexity of binding scenarios. The exceptional high-order and hierarchical encapsulation phenomena suggest a wide host-guest dynamic-fit, enabling conformational adjustment and adaptation beyond the duality of induced-fit and conformational selection in protein interactions. A critical inspection of the host-guest binding events in solution has been performed by NMR and ESI-MS spectra, highlighting the importance of acquiring a reliable binding repertoire from different techniques and the uncertainty of quantifying the binding affinities of multiplying guests by an oversimplified method.

Porous supramolecular assemblies constructed by noncovalent interactions are promising for adsorptive purification of methane because of their easy regeneration. However, the poor stability arising from the weak noncovalent interactions has obstructed their practical applications. Here, we report a robust and easily regenerated polyhedron-based cationic framework assembled from a metal-organic square. This material exhibits a very low affinity for CH 4 and N 2 , but captures other competing gases (e.g. C 2 H 6 , C 3 H 8 , and CO 2 ) with a moderate affinity. These results underpin highly selective separation of a range of gas mixtures that are relevant to natural gas and industrial off-gas. Dynamic breakthrough studies demonstrate its practical separation for C 2 H 6 /CH 4 , C 3 H 8 /CH 4 , CO 2 /N 2 , and CO 2 /CH 4 . Particularly, the separation time is ≈11 min g -1 for the C 2 H 6 /CH 4 (15/85 v/v) mixture and ≈49 min g -1 for the C 3 H 8 /CH 4 (15/85 v/v) mixture (under a flow of 2.0 mL min -1 ), respectively, enabling its capability for CH 4 purification from light alkanes., (© 2022 Wiley-VCH GmbH.)