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Abstract Achieving precise and controllable hierarchical self-assembly of functional nanoclusters within crystal lattices to create distinct architectures is of immense significance, yet it creates considerable challenges. Here we successfully synthesized a silver nanowheel Ag40, along with its optically pure enantiomers S-/R-Ag40. Each species possesses an internal nanospace and exhibits host-guest interactions. These structures are constructed from primary building blocks (Ag9). By manipulating the surface anions and guest molecules, the nanowheels function as secondary building blocks, spontaneously organizing into complex double- and triple-helical crystalline superstructures or one-dimensional chains {Ag41} n through conformational matching and diverse noncovalent interactions. Moreover, we demonstrate that the water-mediated complex specifically assembled with uridine monophosphate nucleotides, resulting in chiral assemblies of Ag40 that exhibit chiroptical activity for specific recognition. Our findings provide insights into the efficient construction of assemblies with hollow frameworks and propose strategies for superstructure engineering by manipulating surface motifs.

Having control over the chirality of metal nanoclusters is challenging. Here, the authors report the deracemization of silver nanoclusters and monitor the chiroptical responses.

Achieving precise and controllable hierarchical self-assembly of functional nanoclusters within crystal lattices to create distinct architectures is of immense significance, yet it creates considerable challenges. Here we successfully synthesized a silver nanowheel Ag40, along with its optically pure enantiomers S-/R-Ag40. Each species possesses an internal nanospace and exhibits host-guest interactions. These structures are constructed from primary building blocks (Ag9). By manipulating the surface anions and guest molecules, the nanowheels function as secondary building blocks, spontaneously organizing into complex double- and triple-helical crystalline superstructures or one-dimensional chains {Ag41}n through conformational matching and diverse noncovalent interactions. Moreover, we demonstrate that the water-mediated complex specifically assembled with uridine monophosphate nucleotides, resulting in chiral assemblies of Ag40 that exhibit chiroptical activity for specific recognition. Our findings provide insights into the efficient construction of assemblies with hollow frameworks and propose strategies for superstructure engineering by manipulating surface motifs. Achieving precise and controllable hierarchical self-assembly of nanoclusters within crystal lattices is of immense significance yet remains challenging. Here the authors synthesize a silver nanowheel Ag40, along with its optically pure enantiomers S-/R-Ag40, and characterize its self-assembly into double- and triple-helical superstructures. [ABSTRACT FROM AUTHOR]

Incorporating dual fluorescence and phosphorescence into a single matrix is attractive for oxygen sensing, but material design is challenging. Here the authors achieve dual fluorescence-phosphorescence from a single linker chromophore in a silver chalcogenolate-cluster-based metal-organic framework.

Abstract Recently, novel core–shell MOF@COF hybrids display excellent performance in various fields because of their inherited advantages from their parent MOFs and/or COFs. However, it is still a grand challenge to adjust the morphology of MOFs and/or COFs for consequent performance improvement. Herein, a Ti‐MOF@TpTt hybrid coated with ultra‐thin COF nanobelt, which is different from the fibrillar‐like parent COF, is successfully synthesized through a sequential growth strategy. The as‐obtained Pd decorated Ti‐MOF@TpTt catalyst exhibits much higher photocatalytic performance than those of Ti‐MOF, TpTt‐COF, and Ti‐MOF@TpTt hybrids with fibrillar‐like COF shell for the photocatalytic cascade reactions of ammonia borane (AB) hydrolysis and nitroarenes hydrogenation. These can be attributed to its high BET surface area, core–shell structure, and type II heterojunction, which offers more accessible active sites and improves the separation efficiency of photo‐generated carriers. Finally, the possible mechanisms of the cascade reaction are also proposed to well explain the improved performance of this photocatalytic system. This work presents a constructive route for designing core–shell MOF@COF hybrids with controllable morphology adjustment of COF shell, leading to the improved photocatalytic ability to broaden the applications of MOF/COF hybrid materials.

Abstract An atom‐precise Cu0‐containing copper cluster, Cu14(C2B10H10S2)6(CH3CN)8 (abbreviated as Cu14‐8CH3CN) is reported, which is synthesized via a simultaneous reduction strategy and fully characterized by single‐crystal X‐ray diffraction, ESI‐TOF‐MS, and X‐ray photoelectron spectroscopy. Cu14‐8CH3CN is the only copper cluster that has a virtually identical silver structural analog, i.e., Ag14(C2B10H10S2)6(CH3CN)8 (hereafter as Ag14‐8CH3CN). Nevertheless, density functional theory calculations reveal that the electronic structure of Cu14‐8CH3CN differs significantly from the superatom electronic configuration of Ag14‐8CH3CN. Moreover, Cu14‐8CH3CN shows room‐temperature luminescence and good electrocatalytic activities in the ethanol oxidation reaction and detection of H2O2. This pair of unprecedented analogous molecular nanoscale systems offer an ideal platform to investigate the fundamental differences between copper and silver in terms of catalytic activity and optical properties.

The stability of perovskite thin films and devices depends on a number of environmental factors, amongst which humidity. Here, Longet al. develop a synthetic route using a nonstoichiometric acid-base reaction to prepare films stable in humid environments for two months.