Epitaxial Growth of Silver Clusters from Ag57 to Ag72 via Laminating Multiple Different Anion Templates.

The established capability of anion templates in precisely manipulating the size, geometry, and function of metal clusters is well acknowledged. However, the development of a systematic methodology for orchestrating the assembly of silver clusters, particularly those encompassing multiple distinct types of anion templates, remains elusive due to the formidable synthetic challenge. In this work, we report two novel silver clusters, Ag57 and Ag72, using two and three different anion templates, respectively.

Buckling cluster-based H-bonded icosahedral capsules and their propagation to a robust zeolite-like supramolecular framework.

Hydrogen-bonded assembly of multiple components into well-defined icosahedral capsules akin to virus capsids has been elusive. In parallel, constructing robust zeolitic-like cluster-based supramolecular frameworks (CSFs) without any coordination covalent bonding linkages remains challenging. Herein, we report a cluster-based pseudoicosahedral H-bonded capsule Cu, which is buckled by the self-organization of judiciously designed constituent copper clusters and anions.

A route to metalloligands consolidated silver nanoclusters by grafting thiacalix[4]arene onto polyoxovanadates.

Metalloligands provide a potent strategy for manipulating the surface metal arrangements of metal nanoclusters, but their synthesis and subsequent installation onto metal nanoclusters remains a significant challenge. Herein, two atomically precise silver nanoclusters {Ag[(TC4A)(VO)](CyS)} (Ag14) and {AgS[(TC4A)(VO)](CyS)(PhCOO)Cl(SO)(DMF)·6DMF} (Ag43) are synthesized by controlling reaction temperature (HTC4A = p-tert-butylthiacalix[4]arene). Interestingly, the 3D scaffold-like [(TC4A)(VO)] metalloligand in Ag14 and 1D arcuate [(TC4A)(VO)] metalloligand in Ag43 exhibit a dual role that is the internal polyoxovanadates as anion template and the surface TC4A as the passivating agent.

Dicarboxylic Acids Induced Tandem Transformation of Silver Nanocluster.

Structural transformation of metal nanoclusters (NCs) is of great ongoing interest regarding their synthesis, stability, and reactivity. Although sporadic examples of cluster transformations have been reported, neither the underlying transformation mechanism nor the intermediates are unambiguous. Herein, we have synthesized a flexible 54-nuclei silver cluster () by combining soft (BuC≡C) and hard (PrCOO) ligands.

Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu Nanoclusters.

Accurate identifying and in-depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect-activity relationships. Yet, atomically precise coinage-metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed-ligand strategy to synthesizing an intrinsically chiral and metal-deficient copper hydride-rich NC [Cu H (PET) (TPP) ] (Cu H ).

Regulating the assembly and expansion of the silver cluster from the Ag to Ag nanowheel driven by heteroanions.

Precise control over the shape and size of metal nanoclusters through anion template-driven self-assembly is one of the key scientific goals in the nanocluster community, however, it is still not understood comprehensively. In this work, we report the controllable synthesis and atomically precise structures of silver nanowheels Ag37 and Ag46, using homo (Cl ions) and heteroanion (Cl and CrO ions) template strategies, along with macrocyclic -phenyl-thiacalix[4]arene and small PrS ligands. Structural analyses revealed that in Ag37, Cl ions serve as both local and global templates, whereas CrO ions function as local and Cl ions as global templates in Ag46, resulting in a pentagonal nanowheel (Ag37) and a hexagonal (Ag46) nanowheel.

Ag Nanoclusters with Thermally Activated Delayed Fluorescence Protected by Ag/Cyanurate/Phosphine Metallamacrocyclic Monolayers through In-Situ Ligand Transesterification.

The composition of protection monolayer exerts great influence on the molecular and electronic structures of atomically precise monolayer protected metal nanoclusters. Four isostructural Ag/cyanurate/phosphine metallamacrocyclic monolayer protected Ag nanoclusters are synthesized by kinetically controlled in-situ ligand formation-driven strategy. These eight-electron superatomic silver nanoclusters feature an unprecedented interfacial bonding structure with diverse E-Ag (E=O/N/P/Ag) interactions between the Ag core and metallamacrocyclic monolayer, and displays thermally activated delayed fluorescence (TADF), benefiting from their distinct donor-acceptor type electronic structures.

Real-Time Fluorescent Monitoring of Kinetically Controlled Supramolecular Self-Assembly of Atom-Precise Cu Nanocluster.

Kinetically stable and long-lived intermediates are crucial in monitoring the progress and understanding of supramolecular self-assembly of diverse aggregated structures with collective functions. Herein, the complex dynamics of an atomically precise Cu nanocluster [Cu ( BuC H S) (PPh ) ] (Cu8a) is systematically investigated. Remarkably, by monitoring the aggregation-induced emission (AIE) and electron microscopy of the kinetically stable intermediates in real time, the directed self-assembly (DSA) process of Cu8a is deduced.

Observation of a bcc-like framework in polyhydrido copper nanoclusters.

Cu is well-known to adopt a face-centered cubic (fcc) structure in the bulk phase. Ligand-stabilized Cu nanoclusters (NCs) with atomically precise structures are an emerging class of nanomaterials. However, it remains a great challenge to have non-fcc structured Cu NCs.

Precise Implantation of an Archimedean Ag@Cu Cuboctahedron into a Platonic CuBis(diphenylphosphino)hexane Tetrahedron.

Precision loading of nanoclusters in confined spaces, which has been enthusiastically pursued in the scientific realm, is still associated with some mysteries of "how", "when", and "why". Here, we isolated two similar heterometallic cluster-in-cage compounds, [Ag@CuS@Cu(dpph)]X (X = OH, and X = PF, ; = ), by use of an antigalvanic reaction between organometallic [PhC≡CCu] and PhCSH with elemental silver. Both compounds are formed by fitting an Archimedean Ag@Cu cuboctahedral cluster into a Platonic Cu(dpph) tetrahedral cage [dpph = bis(diphenylphosphino)hexane].

Polymorphism in Atomically Precise Cu Nanocluster Incorporating Tetrahedral [Cu] Kernel.

Because of the typical instability of copper nanoclusters, atom-precise structural elucidation of these nanoclusters has remained elusive. Herein, we report an air- and moisture-stable 23-copper nanocluster ( or ) isolated from the reaction of Cu(CFCOO), BuC≡CH, Cu powder, and PhSiH using a gradient reduction (Cu → Cu → Cu) strategy (GRS), which is competent for controlling the kinetics of the reduction reaction, thus avoiding formation of pure Cu complexes or large Cu nanoparticles. The solid-state structure of the Cu nanocluster shows a rare [Cu] tetrahedral kernel surrounded by an outer Cu shell, which is protected by BuC≡C and CFCOO ligands.