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Superbugs are bacteria that have grown resistant to most antibiotics, seriously threating the health of people. Silver (Ag) nanoparticles are known to exert a wide‐spectrum antimicrobial property, yet remains challenging against superbugs. Here, Ag clusters are assembled using porphyrin‐based linkers and a novel framework structure (Ag9‐AgTPyP) is produced, in which nine‐nuclearity Ag9 clusters are uniformly separated by Ag‐centered porphyrin units (AgTPyP) in two dimensions, demonstrating open permeant porosity. Ag9‐AgTPyP eliminates over 99.99999% and 99.999% methicillin‐resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa (P. aeruginosa) within 2 h upon visible‐light irradiation, which are superior to a majority of bacteria inactivation photocatalysts. The novel‐established long‐term charge‐transfer states from AgTPyP to adjacent Ag9 cluster that has preferential affinity to O2 greatly promote reactive oxygen species (ROS) production efficiency; and its unique framework accelerates the ROS transportation. Personal protective equipment (masks and protective suits) incorporating Ag9‐AgTPyP film also shows excellent performances against superbugs. This superbugs‐killing efficiency is unprecedented among silver complexes and porphyrin derivatives. Utilizing efficient photogenerated electrons and holes between metal cluster and linkers can open up new interests of research in photocatalytic areas. Silver cluster‐porphyrin assembled materials (Ag9‐AgTPyP) are demonstrated as advanced bioprotective materials for combating superbacteria, in which the photogenerated charge efficiently transfers from AgTPyP to adjacent Ag9 cluster that has preferential affinity to O2 and greatly promoting reactive oxygen species production.

The weakly coordinated anionic nitrate ligands in a centrosymmetric Ag20 cluster are replaced in a stepwise manner by chiral amino acids and two achiral luminescent sulfonic‐group‐containing ligands while nearly maintaining the original silver(I) cage structure. This surface engineering enables the atomically precise Ag20 clusters to exhibit the high‐efficiency synergetic effects of chirality and fluorescence, producing rare circularly polarized luminescence among the metal clusters with a large dissymmetry factor of (|glum|) ≈ 5 × 10−3. This rational approach using joint functional ligands further opens a new avenue to diverse multifunctional metal clusters for promising applications. A step‐by‐step surface modification approach is proposed to synthesize multifunctional silver(I) nanoclusters. By combining both chiral and luminescent organic ligands on the Ag20 surface, the circularly polarized luminescence reactivity is rationally designed for silver(I) cluster compounds. This rational approach using joint functional ligands further opens a new avenue to diverse multifunctional metal clusters for promising applications.

Establishing the correlation between inter-cluster assembly and auxiliary ligands at the atomic level is crucial for the development of metal cluster science. In this work, we report the successful preparation and characterization of three Ag clusters, discrete 0-D Ag 51 S 6 Cl 3 ( i PrS) 21 (TsO) 15 CH 3 CN ( 0-D Ag 51 , i PrS − = isopropanethiolate, TsO − = toluenesulfonate), 1-D {Ag 38 S 4 ( i PrS) 18 (PhCOO) 12 } n ( 1-D Ag 38 , PHCOO − = benzoate), and 2-D {Ag 20 (SO 4 )Cl 2 ( i PrS) 10 (NO 3 ) 6 } n ( 2-D Ag 20 ), using a delicate auxiliary-ligand-induced strategy. Structural analyses reveal that the types of auxiliary ligands can readily affect the structure and dimensionality of resulting Ag clusters. The addition of different surface auxiliary ligands from TsO − to PhCOO − and then to NO 3 − leads to the formation of 0-D Ag 51 to 1-D Ag 38 and then to 2-D Ag 20 clusters under otherwise identical reaction conditions, respectively. The resulting Ag clusters exhibited structure-related optical/luminescence properties and distinct bathochromic shifts as revealed by the temperature-dependent luminescence and single-crystal X-ray diffraction studies.

The development of stimuli‐responsive circularly polarized luminescence (CPL) materials is quite attractive but challenging. Here, a pair of atomically precise enantiomers R/S‐Ag20 nanoclusters has been synthesized using chiral acid ligands. And then, stimuli‐responsive CPL materials were developed by assembling the chiral silver nanoclusters with an achiral bridging ligand. The atomically precise silver cluster‐assembled materials produce CPL with a dissymmetry factor (|glum|) of 1 × 10−3, through the high‐efficiency chiral induction process. More interestingly, the single CPL band at room temperature could quickly transform into highly separated dual CPL emissions at low temperature. This study provides a new strategy for the rational functionalization of chiral silver clusters in preparing cluster‐based CPL emitters and enriches the types of stimuli‐responsive CPL materials. The temperature‐triggered dynamic circularly polarized luminescence materials were constructed by the coordination assembly of chiral silver nanoclusters and luminophor linkers.

Metal nanoclusters (NCs) are gaining much attention in nanoscale materials research because they exhibit size-specific physicochemical properties that are not observed in the corresponding bulk metals. Among them, silver (Ag) NCs can be precisely synthesized not only as pure Ag NCs but also as anion-templated Ag NCs. For anion-templated Ag NCs, we can expect the following capabilities: 1) size and shape control by regulating the central anion (anion template); 2) stabilization by adjusting the charge interaction between the central anion and surrounding Ag atoms; and 3) functionalization by selecting the type of central anion. In this review, we summarize the synthesis methods and influences of the central anion on the geometric structure of anion-templated Ag NCs, which include halide ions, chalcogenide ions, oxoanions, polyoxometalate, or hydride/deuteride as the central anion. This summary provides a reference for the current state of anion-templated Ag NCs, which may promote the development of anion-templated Ag NCs with novel geometric structures and physicochemical properties.

Chiral metal‐organic frameworks (MOFs) are usually endowed by chiral linkers and/or guests. The strategy using chiral secondary building units in MOFs for solving the trade‐off of circularly polarized luminescence (CPL)‐active materials, high photoluminescence quantum yields (PLQYs) and high dissymmetry factors (|glum|) has not been demonstrated. This work directionally assembles predesigned chiral silver clusters with ACQ linkers through reticular chemistry. The nanoscale chirality of the cluster transmits through MOF's framework, where the linkers are arranged in a quasi‐parallel manner and are efficiently isolated and rigidified. Consequently, this backbone of chiral cluster‐based MOFs demonstrates superb CPL, high PLQYs of 50.3%, and |glum| of 1.2 × 10−2. Crystallographic analyses and DFT calculations show the quasi‐parallel arrangement manners of emitting linkers leading to a large angle between the electric and magnetic transition dipole moments, boosting CPL response. As compared, an ion‐pair‐direct assembly without interactions between linkers induces one‐ninth |glum| and one‐sixth PLQY values, further highlighting the merits of directional arrangement in reticular nets. In addition, a prototype CPL switching fabricated by a chiral framework is controlled through alternating ultraviolet and visible light. This work is expected to inspire the development of reticular chemistry for high‐performance chiroptical materials. Chiral transfer and circularly polarized luminescence activity are successfully achieved by assembling ACQ molecules with chiral Ag clusters in chiral silver cluster‐based assembled materials. The chiral reticular self‐assembly exhibits markedly enhanced luminescence efficiency and glum values compared to those of the ion‐pair‐direct assembly through a well‐defined spatial arrangement and highly efficient synergy.

Aggregation‐induced emission (AIE) and thermally activated delayed fluorescence (TADF) are two optoelectronic properties with great potential for applications. However, metal nanoclusters exhibiting both AIE and TADF characteristics have not been extensively studied. This study investigates a binary cocrystal system based on silver nanoclusters—Ag6(Et2NCS2)6·[Ag11(AdmS)3(Et2NCS2)6]2 (1‐Ag6·(Ag11)2), aiming to explore the synergistic effects between flexible‐alkyl dithiol and rigid monothiol ligands. Due to the introduction of Ag6 structures, the system exhibits enhanced stability and modulated optical properties. The binary tricluster 1‐Ag6·(Ag11)2 demonstrates significant AIE behavior, with an approximately 15‐fold increase in intensity when the water volume fraction (fw) is 60%. Single‐crystal X‐ray diffraction analysis indicates that the enhanced AIE effect originates from intercluster hydrogen bonding interactions, which drive the self‐assembly of sub‐clusters and form hierarchical structures, thereby suppressing ligand rotation. In addition, the system exhibits the TADF phenomenon in the temperature range of 100−175 K. In order to further investigate the effect of ligand variations on optical properties, two unitary clusters, Ag11(AdmS)3(Et2NCS2)6 (2‐Ag11‐AS) and Ag11(tBuS)3(Et2NCS2)6 (3‐Ag11‐BS), are synthesized, and their roles in regulating optoelectronic properties are explored through ligand exchange reactions. This study provides important insights for the development of efficient luminescent materials with AIE and TADF properties, highlighting the critical roles of ligand exchange and structural configuration. Cocrystallizing Ag6 and Ag11 structures into supramolecular assembly in a 1: 2 ratio results in a binary tricluster Ag6·(Ag11)2, exhibiting both significant AIE and TADF properties. The separated two unitary Ag11 clusters confirm the critical role of Ag11 structures in AIE and TADF behavior, which are regulated by intercluster interactions and molecular rigidity.

Isolating reductive silver kernel from shell is a challenging task but is quite important to understand the embryonic form during the formation of silver nanoclusters. The intercalation of suitable anionic species may be of benefit for passivating then capturing such highly active kernel. Herein, we successfully isolated a novel silver thiolate nanocluster [Ag 13 @Ag 76 S 16 (CyhS) 42 ( p -NH 2 -PhAsO 3 ) 4 ] 3+ ( SD / Ag89a , CyhSH = cyclohexanethiol) that contains a well-isolated icosahedral Ag 13 kernel passivated by four AgS 4 7− tetrahedra and four p -NH 2 PhAsO 3 2− piercing from outer Ag 72 shell. Of note, this Ag 13 kernel is the largest isolable subvalent silver kernel beneath the silver shell with extremely legible core-shell boundary ever before and represents a precise embryonic model formed in the reducing Ag(I) to Ag(0) followed by aggregating to large silver nanoparticles. The reductive role of DMF and the introduction of anionic passivation layer (APL) synergistically modulate the reduction kinetics, facilitating the capture of ultrasmall subvalent silver kernel. SD / Ag89a emits in near infrared (NIR) region ( λ em = 800 nm) at low temperature. The synthetic strategy shown in this work opens up new opportunities for precisely capturing and recognizing diverse reductive silver kernels in different systems.

A pair of chiral nanocluster complexes were formed by the host−guest interaction between the enantiomeric 2,6-helic[6]arenes and nanocluster Ag20. The formation and stability of the nanocluster complexes were experimentally and theoretically confirmed. Meanwhile, the chiral nanocluster complexes exhibited enhanced luminescence and induced CD signals at room temperature in the solid state, revealing the stable complexation and chirality transfer from the chiral macrocycles to the nanocluster Ag20.

The bright luminescence of silver clusters in glass have potential applications in solid-state lighting, optical memory, and spectral converters. In this work, luminescent silver clusters were formed in the bulk of photo-thermo-refractive glass (15Na2O-5ZnO-2.9Al2O3-70.3SiO2-6.5F, mol.%) doped with different Ag2O concentrations from 0.01 to 0.05 mol.%. The spontaneous formation of plasmonic nanoparticles during glass synthesis was observed at 0.05 mol.% of Ag2O in the glass composition, limiting the silver concentration range for cluster formation. The luminescence of silver clusters was characterized by steady-state and time-resolved spectroscopy techniques. The rate constants of fluorescence, phosphorescence, intersystem crossing, and nonradiative deactivation were estimated on the basis of an experimental study. A comparison of the results obtained for the photophysical properties of luminescent silver clusters formed in the ion-exchanged layers of photo-thermo-refractive glass is provided.