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).
View Article and Find Full Text PDFCoinage 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.
View Article and Find Full Text PDFDetailed 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.
View Article and Find Full Text PDFChiral 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.
View Article and Find Full Text PDFGreen ammonia synthesis through electrocatalytic nitrate reduction reaction (eNORR) can serve as an effective alternative to the traditional energy-intensive Haber-Bosch process. However, achieving high Faradaic efficiency (FE) at industrially relevant current density in neutral medium poses significant challenges in eNORR. Herein, with the guidance of theoretical calculation, a metallic CoNi-terminated catalyst is successfully designed and constructed on copper foam, which achieves an ammonia FE of up to 100% under industrial-level current density and very low overpotential (-0.
View Article and Find Full Text PDFLigand-protected metal clusters possess hybrid properties that seamlessly combine an inorganic core with an organic ligand shell, imparting them exceptional chemical flexibility and unlocking remarkable application potential in diverse fields. Leveraging chemical flexibility to expand the library of available materials and stimulate the development of new functionalities is becoming an increasingly pressing requirement. This Review focuses on the origin of chemical flexibility from the structural analysis, including intra-cluster bonding, inter-cluster interactions, cluster-environments interactions, metal-to-ligand ratios, and thermodynamic effects.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2024
The dual emission (DE) characteristics of atomically precise copper nanoclusters (Cu NCs) are of significant theoretical and practical interest. Despite this, the underlying mechanism driving DE in Cu NCs remains elusive, primarily due to the complexities of excited state processes. Herein, a novel [Cu(PPh)(C≡C-p-NHCH)]PF (Cu) NC, shielded by alkynyl and exhibiting DE, was synthesized.
View Article and Find Full Text PDFControlled 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.
View Article and Find Full Text PDFCrystalline frameworks represent a cutting-edge frontier in material science, and recently, there has been a surge of interest in energetic crystalline frameworks. However, the well-established porosity often leads to diminished output energy, necessitating a novel approach for performance enhancement. Thiol-yne coupling, a versatile metal-free click reaction, has been underutilized in crystalline frameworks.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2024
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.
View Article and Find Full Text PDFMaterials 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.
View Article and Find Full Text PDFChiroptical activities arising in nanoclusters (NCs) are emerging as one of the most dynamic areas of modern science. However, devising an overarching strategy that is capable of concurrently enhancing the photoluminescence (PL) and circularly polarized luminescence (CPL) of metal NCs remains a formidable challenge. Herein, gold and silver nanoclusters (AuNCs, AgNCs) are endowed with CPL, for the first time, through a universal host-guest approach─centered around perturbing a chiral microenvironment within chiral hosts, simultaneously enhancing emissions.
View Article and Find Full Text PDFUnderstanding the fundamentals and applications of chirality relies substantially on the amplification of chirality through hierarchical assemblies involving various weak interactions. However, a notable challenge remains for metal clusters chiral assembly driven by halogen bonding, despite their promising applications in lighting, catalysis, and biomedicine. Here, we used halogen bonding-driven assembly to achieve a hierarchical degree of achiral emissive clusters.
View Article and Find Full Text PDFCircularly 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.
View Article and Find Full Text PDFThree-component dehydrogenative coupling reactions represent important and practical methodologies for forging new C-N bonds and C-C bonds. Achieving highly all-in-one dehydrogenative coupling functionalization by a single catalytic system remains a great challenge. Herein, we develop a rigid-flexible-coupled copper cluster [Cu(NHC)(PF)] (CuNC) using a tridentate N-heterocyclic carbene ligand.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFBright and efficient chiral coinage metal clusters show promise for use in emerging circularly polarized light-emitting materials and diodes. To date, highly efficient circularly polarized organic light-emitting diodes (CP-OLEDs) with enantiopure metal clusters have not been reported. Herein, through rational design of a multidentate chiral N-heterocyclic carbene (NHC) ligand and a modular building strategy, we synthesize a series of enantiopure Au(I)-Cu(I) clusters with exceptional stability.
View Article and Find Full Text PDFThe propulsion of photocatalytic hydrogen (H ) production is limited by the rational design and regulation of catalysts with precise structures and excellent activities. In this work, the [MoOS ] unit is introduced into the Cu clusters to form a series of atomically-precise Mo -Cu bimetallic clusters of [Cu (MoOS ) (C H (CH )S) (P(C H -R) ) ] ⋅ xCH CN (R=H, CH , or F), which show high photocatalytic H evolution activities and excellent stability. By electron push-pull effects of the surface ligand, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of these Mo -Cu clusters can be finely tuned, promoting the resultant visible-light-driven H evolution performance.
View Article and Find Full Text PDFLuminescent metal-organic cages are of great interest in contemporary research; however, their designed synthesis remains challenging. Here, we created metal-cluster-derived spacers, where emissive -symmetric Cu clusters have three arms modified by benzene alkynyl ligands, which are terminally functionalized by extensile -COOH and 15-crown-5-ether groups with directional coordination ability. Through vertex orientation, -COOH-functionalized cluster-based spacers coassembled with paddle-wheel Cu(I)Zn(II)(COO) nodes in 3+3 mode, generating an emissive cubic cage, which subsequently gave another distorted cubic cage by synthetic modification on the nodes.
View Article and Find Full Text PDFChiral 2D organic-inorganic hybrid perovskites (C-2D-OIHPs) with circularly polarized luminescence (CPL) have important promising applications in optical, electronic, and chiroptoelectronic devices. Herein, we report enantiomeric crystals of /-FMBA)PbBr. (FMBA = 4-fluorophenethylamine), which demonstrated bright room-temperature CPL emission.
View Article and Find Full Text PDFChiral 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.
View Article and Find Full Text PDFSuperstructures 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).
View Article and Find Full Text PDFChiral 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.
View Article and Find Full Text PDFMetal-containing clusters have attracted increasing attention over the past 2-3 decades. This intense interest can be attributed to the fact that these discrete metal aggregates, whose atomically precise structures are resolved by single-crystal X-ray diffraction (SCXRD), often possess intriguing geometrical features (high symmetry, aesthetically pleasing shapes and architectures) and fascinating physical properties, providing invaluable opportunities for the intersection of different disciplines including chemistry, physics, mathematical geometry and materials science. In this review, we attempt to reinterpret and connect these fascinating clusters from the perspective of Platonic and Archimedean solid characteristics, focusing on highly symmetrical and complex metal-containing (metal = Al, Ti, V, Mo, W, U, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, lanthanoids (Ln), and actinoids) high-nuclearity clusters, including metal-oxo/hydroxide/chalcogenide clusters and metal clusters (with metal-metal binding) protected by surface organic ligands, such as thiolate, phosphine, alkynyl, carbonyl and nitrogen/oxygen donor ligands.
View Article and Find Full Text PDF