Hierarchical assembly of Ag nanowheel ranging from building blocks to diverse superstructure regulation.

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 Ag, along with its optically pure enantiomers S-/R-Ag Each species possesses an internal nanospace and exhibits host-guest interactions. These structures are constructed from primary building blocks (Ag).

Organic Thiolate as Multifunctional Salt for Rechargeable Lithium-Sulfur Batteries.

The practical application of lithium-sulfur (Li-S) batteries is hindered by the severe shuttle effect of soluble polysulfide intermediates and the unstable lithium anode interface. Conventional lithium salts (e.g.

Atomically Precise Ternary Cluster: Polyoxometalate Cluster Sandwiched by Gold Clusters Protected by N-Heterocyclic Carbenes.

Coinage metal (Au, Ag, Cu) cluster and polyoxometalate (POM) cluster represent two types of subnanometer "artificial atoms" with significant potential in catalysis, sensing, and nanomedicine. While composite clusters combining Ag/Cu clusters with POM have achieved considerable success, the assembly of gold clusters with POM is still lagging. Herein, we first designedly synthesized two cluster structural units: an AuO cluster stabilized by diverse N-heterocyclic carbene (NHC) ligands and an amine-terminated POM linker.

Influence of the substituents of the thiol ligand on the optical properties of AuCu.

Detailed photophysical processes of two AuCu clusters with different substituents (-F or -C(CH)) of the thiol ligand were studied in this work. The electronic effect of the substituents led to structural shrinkage, thus enhancing the luminous intensity. The internal conversion (IC) and intersystem crossing (ISC) rates in the AuCu14-C(CH3)3 crystal were slower compared with the AuCu14-F crystal, which was caused by the steric effect.

Carborane-Cluster-Wrapped Copper Cluster with Cyclodextrin-like Cavities for Chiral Recognition.

Chiral atomically precise metal clusters, known for their remarkable chiroptical properties, hold great potential for applications in chirality recognition. However, advancements in this field have been constrained by the limited exploration of host-guest chemistry, involving metal clusters. This study reports the synthesis of a chiral Cu(CBHS) (denoted as Cu@CB, where CBHSH = 9,12-(HS)-1,2--carborane) cluster by an achiral carboranylthiolate ligand.

Construction of novel Ag(0)-containing silver nanoclusters by regulating auxiliary phosphine ligands.

Controlled synthesis of metal clusters through minor changes in surface ligands holds significant interest because the corresponding entities serve as ideal models for investigating the ligand environment's stereochemical and electronic contributions that impact the corresponding structures and properties of metal clusters. In this work, we obtained two Ag(0)-containing nanoclusters (Ag17 and Ag32) with near-infrared emissions by regulating phosphine auxiliary ligands. Ag17 and Ag32 bear similar shells wherein Ag17 features a trigonal bipyramid Ag kernel while Ag32 has a bi-icosahedral interpenetrating an Ag kernel.

Rapid Construction of Double Crystalline Prussian Blue Analogue Hetero-Superstructure.

The controllable construction of complex metal-organic coordination polymers (CPs) merits untold scientific and technological potential, yet remains a grand challenge of one-step construction and modulating simultaneously valence states of metals and topological morphology. Here, a thiocyanuric acid (TCA)-triggered strategy is presented to one-step rapid synthesis a double-crystalline Prussian blue analogue hetero-superstructure (PBA-hs) that comprises a Co[Fe(CN)] cube overcoated with a KCo[Fe(CN)] shell, followed by eight self-assembled small cubes on vertices. Unlike common directing surfactants, TCA not only acts as a trigger for the fast growth of KCo[Fe(CN)] on the Co[Fe(CN)] phase resulting in a PBA-on-PBA hetero-superstructure, but also serves as a flange-like bridge between them.

Staggered Assembly of a Dimeric Au Cluster: Impacts on Coupling of Geometric Isomerism.

The specific states of aggregation of metal atoms in sub-nanometer-sized gold clusters are related to the different quantum confinement volumes of electrons, leading to novel optical and electronic properties. These volumes can be tuned by changing the relative positions of the gold atoms to generate isomers. Studying the isomeric gold core and the electron coupling between the basic units is fundamentally important for nanoelectronic devices and luminescence; however, appropriate cases are lacking.

X-ray-triggered through-space charge transfer and photochromism in silver nanoclusters.

Materials exhibiting X-ray-induced photochromism have consistently piqued the interest of researchers. Exploring the photochromic properties of such materials is valuable for understanding the structural changes and electron transfer processes that occur under high energy radiation, such as X-ray irradiation. Here, a crystalline silver(I) nanocluster synthesized from -butylacetylene silver was found to have the ability to exhibit color and photoluminescence changes upon exposure to X-ray radiation.

High-Efficiency Pure Blue Circularly Polarized Phosphorescence from Chiral -Heterocyclic-Carbene-Stabilized Copper(I) Clusters.

Circularly polarized luminescence (CPL) materials have attracted considerable attention for their promising applications in encryption, chiral sensing, and three-dimensional (3D) displays. However, the preparation of high-efficiency, pure blue CPL materials remains challenging. In this study, we reported an enantiomeric pair of triangle copper(I) clusters (/) rigidified by employing chiral -heterocyclic carbene (NHC) ligands with two pyridine-functionalized wingtips.

Chiral Hydride Cu Clusters Transform to Superatomic CuAg Clusters: Circularly Polarized Luminescence Lighting.

The manipulation of metal cluster enantiomers and their reconstruction remain challenging. Here, for the first time, we report an enantiomeric pair of hydride copper clusters [CuH(-PEA)](BF) () made using designed chiral ligands. By manipulation of with Ag ions, H ions are released, leading to the reconstruction of 15 Cu atoms.

Thermally Activated Delayed Fluorescence Coinage Metal Cluster Scintillator.

X-ray scintillators are widely used in medical imaging, industrial flaw detection, security inspection, and space exploration. However, traditional commercial scintillators are usually associated with a high use cost because of their substantial toxicity and easy deliquescence. In this work, an atomically precise Au-Cu cluster scintillator () with a thermally activated delayed fluorescence (TADF) property was facilely synthesized, which is environmentally friendly and highly stable to water and oxygen.

Long-Life, High-Rate Rechargeable Lithium Batteries Based on Soluble Bis(2-pyrimidyl) Disulfide Cathode.

Organosulfides are promising candidates as cathode materials for the development of electric vehicles and energy storage systems due to their low-cost and high capacity properties. However, they generally suffer from slow kinetics because of the large rearrangement of S-S bonds and structural degradation upon cycling in batteries. In this paper, we reveal that soluble bis(2-pyrimidyl) disulfide (Pym S ) can be a high-rate cathode material for rechargeable lithium batteries.

Comparative Study on Proton Conductivity and Mechanism Analysis of Two Imidazole Modified Imine-Based Covalent Organic Frameworks.

This work elucidates the potential impact of intramolecular H-bonds within the pore walls of covalent organic frameworks (COFs) on proton conductivity. Employing DaTta and TaTta as representative hosts, it was observed that their innate proton conductivities (σ) are both unsatisfactory and σ(DaTta)<σ(TaTta). Intriguingly, the performance of both imidazole-loaded products, Im@DaTta and Im@TaTta is greatly improved, and the σ of Im@DaTta (0.

Water Network-Augmented Two-State Model for Protein-Ligand Binding Affinity Prediction.

Water network rearrangement from the ligand-unbound state to the ligand-bound state is known to have significant effects on the protein-ligand binding interactions, but most of the current machine learning-based scoring functions overlook these effects. In this study, we endeavor to construct a comprehensive and realistic deep learning model by incorporating water network information into both ligand-unbound and -bound states. In particular, extended connectivity interaction features were integrated into graph representation, and graph transformer operator was employed to extract features of the ligand-unbound and -bound states.

High Performance Dynamic X-ray Flexible Imaging Realized Using a Copper Iodide Cluster-Based MOF Microcrystal Scintillator.

X-ray imaging technology has achieved important applications in many fields and has attracted extensive attentions. Dynamic X-ray flexible imaging for the real-time observation of the internal structure of complex materials is the most challenging type of X-ray imaging technology, which requires high-performance X-ray scintillators with high X-ray excited luminescence (XEL) efficiency as well as excellent processibility and stability. Here, a macrocyclic bridging ligand with aggregation-induced emission (AIE) feature was introduced for constructing a copper iodide cluster-based metal-organic framework (MOF) scintillator.

Activation of Bulk Li S as Cathode Material for Lithium-Sulfur Batteries through Organochalcogenide-Based Redox Mediation Chemistry.

Lithium sulfide (Li S) is considered as a promising cathode material for sulfur-based batteries. However, its activation remains to be one of the key challenges against its commercialization. The extraction of Li from bulk Li S has a high activation energy (E ) barrier, which is fundamentally responsible for the initial large overpotential.

Highly Efficient Circularly Polarized Luminescence from Chiral Au Clusters Stabilized by Enantiopure Monodentate NHC Ligands.

Chiral Au nanoclusters have promising application prospects in chiral sensing, asymmetric catalysis, and chiroptics. However, enantiopure superatomic homogold clusters with crystallographic structures emitting bright circularly polarized luminescence (CPL) remain challenging. In this study, we designed chiral N-heterocyclic carbenes (NHCs), and for the first time enantioselectively synthesized a pair of monovalent cationic superatomic Au clusters.

Smart Reversible Transformations between Chiral Superstructures of Copper Clusters for Optical and Chiroptical Switching.

Superstructures made from nanoscale clusters with new collective properties are promising in high-tech applications; however, chiral superstructures remain elusive, and the limited intercluster coupling effect at room temperature hampers the tailoring of collective properties. Here, we show that from chiral monomeric copper clusters to two enantiomeric pairs of supercrystals with distinct phases, the absorption band edge red-shifts by over 1.3 eV, with photoluminescence and circularly polarized phosphorescence from visible (572 nm) to near-infrared (NIR, 858 nm).

A cyclic organosulfide cathode with ultrastable cycling performance in lithium batteries.

We report a cyclic organosulfide synthesized a condensation reaction. It can be cycled for 1000 times in half cells. Impressively, it can work with lithiated carbon paper as the anode in ether electrolyte in a full cell.

Stepwise Amplification of Circularly Polarized Luminescence in Chiral Metal Cluster Ensembles.

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 (|g |) has not been demonstrated. This work directionally assembles predesigned chiral silver clusters with ACQ linkers through reticular chemistry.

Achiral-Core-Metal Change in Isomorphic Enantiomeric AgAg and AuAg Clusters Triggers Circularly Polarized Phosphorescence.

Understanding how the chiral or achiral section in chiral nanostructures contributes to circularly polarized light emission (CPLE) at the atomic level is of fundamental importance. Here, we report two pairs of atomically precise enantiomers of homosilver () and heterometal () clusters. The geometrical chirality of arises from the chiral ligand and interface consisting of positive moieties of Ag(/-PS).

A phenyl S-Te bond with unique redox activity in dilute electrolyte of a lithium battery.

Phenyl tellurosulfide (PhS-TePh) was used to study the redox activity of the S-Te bond in lithium batteries. PhS-TePh formed a dynamic covalent network during lithiation, which provided a balance between responsiveness and stability to facilitate ion and electron transfer, enabling Li/PhS-TePh cells to achieve stable cycling and excellent rate performance in dilute electrolyte.