Chemical Synthesis of ~1 nm Multilevel Capacitor-like Particles with Atomic Precision.

Can the chemically synthesized nanoparticles act as nanodevices or nanomachines? Herein, we demonstrated this feasibility. A novel nanocluster (ultrasmall nanoparticle) [AuCd(m-MBT)][N(CH)] (AuCd in short, m-MBTH: m-methylbenzenethiol) obtained via developing a synthesis method has a cannula-like structure of the outer shell and an internal sleeve, revealed by single-crystal X-ray diffraction. Natural population analysis (NPA) charge calculations, charge carrier transport of AuCd (during which an intra-nanocluster anti-galvanic reaction was observed) after unneutral charging using NaBH as well as voltammetry proved the capacitor-like character of AuCd.

Concomitant Near-Infrared Photothermy and Photoluminescence of Rod-Shaped Au(PET) and Au(PET) Synthesized Concurrently.

Gold nanoclusters exhibiting concomitant photothermy (PT) and photoluminescence (PL) under near-infrared (NIR) light irradiation are rarely reported, and some fundamental issues remain unresolved for such materials. Herein, we concurrently synthesized two novel rod-shaped Au nanoclusters, Au(PET) and Au(PET) (PET = 2-phenylethanethiolate), and precisely revealed that their kernels were 4 × 4 × 6 and 5 × 4 × 6 face-centered cubic (fcc) structures, respectively, based on the numbers of Au layers in the [100], [010], and [001] directions. Following the structural growth mode from Au(PET) to Au(PET), we predicted six more novel nanoclusters.

Bottom-Up Construction of Metal-Organic Framework Loricae on Metal Nanoclusters with Consecutive Single Nonmetal Atom Tuning for Tailored Catalysis.

The introduction of single or multiple heterometal atoms into metal nanoparticles is a well-known strategy for altering their structures (compositions) and properties. However, surface single nonmetal atom doping is challenging and rarely reported. For the first time, we have developed synthetic methods, realizing "surgery"-like, successive surface single nonmetal atom doping, replacement, and addition for ultrasmall metal nanoparticles (metal nanoclusters, NCs), and successfully synthesized and characterized three novel bcc metal NCs AuI(S-Adm), AuS(S-Adm), and AuIS(S-Adm) (S-Adm: 1-adamantanethiolate).

Controlled Sequential Doping of Metal Nanocluster.

Atomically precise doping of metal nanoclusters provides excellent opportunities not only for subtly tailoring their properties but also for in-depth understanding of composition (structure)-property correlation of metal nanoclusters and has attracted increasing interest partly due to its significance for fundamental research and practical applications. Although single and multiple metal atom doping of metal nanoclusters (NCs) has been achieved, sequential single-to-multiple metal atom doping is still a big challenge and has not yet been reported. Herein, by introducing a second ligand, a novel multistep synthesis method was developed, controlled sequential single-to-multiple metal atom doping was successfully achieved for the first time, and three doped NCs AuCd(p-MBT)(PPh), AuCd(p-MBT)(PPh), and [AuCd(p-MBT)] (p-MBTH: -methylbenzenethiol) were obtained, including two novel NCs that were precisely characterized via mass spectrometry, single-crystal X-ray crystallography, and so forth.

Pd Nanocluster with Nonmetal-to-Metal- Ring Coordination and Promising Photothermal Conversion Efficiency.

Constructing ambient-stable, single-atom-layered metal-based materials with atomic precision and understanding their underlying stability mechanisms are challenging. Here, stable single-atom-layered nanoclusters of Pd were synthesized and precisely characterized through electrospray ionization mass spectrometry and single-crystal X-ray crystallography. A pseudo-pentalene-like Pd unit was found in the nanocluster, interacting with two syn PPh units through nonmetal-to-metal -ring coordination.

Lattice Compression Revealed at the ≈1 nm Scale.

Lattice tuning at the ≈1 nm scale is fascinating and challenging; for instance, lattice compression at such a minuscule scale has not been observed. The lattice compression might also bring about some unusual properties, which waits to be verified. Through ligand induction, we herein achieve the lattice compression in a ≈1 nm gold nanocluster for the first time, as detected by the single-crystal X-ray crystallography.

Sandwich-Kernelled AgCu Nanoclusters with Golden Ratio Geometry and Promising Photothermal Efficiency.

Metal nanoclusters have recently attracted extensive interest from the scientific community. However, unlike carbon-based materials and metal nanocrystals, they rarely exhibit a sheet kernel structure, probably owing to the instability caused by the high exposure of metal atoms (particularly in the relatively less noble Ag or Cu nanoclusters) in such a structure. Herein, we synthesized a novel AgCu nanocluster with a sandwich-like kernel (diameter≈0.

Regulating the Electronic Structure of Metal Nanoclusters by Longitudinal Single-Dithiolate Substitution.

It is significant but challenging to understand the property evolution of metal nanoclusters by orientated regulation of the electronic structure. Previous research has demonstrated that the optical properties of metal nanoclusters with anisotropic structures are greatly impacted by their longitudinal electronic structure. However, the manipulation of optical properties of metal nanoclusters by regulating their electronic structure through longitudinal dithiolate substitutions has not yet been reported.

Surface Site-Specific Replacement for Catalysis Selectivity Switching.

Surface atom replacement in materials without other composition/structure changes is challenging but is important for fundamental scientific research and for practical applications. In particular, for nanoparticles including nanoclusters, surface metal site-specific replacement with atomic precision has not yet been achieved. In this study, we for the first time achieved surface site-specific antigalvanic replacement with the remaining composition/structure and surface replacement-dependent selectivity in the electrocatalytic reduction of CO.

Synthesizing Photoluminescent Au (SCH Ph- Bu) Nanoclusters with Structural Features by Using a Combined Method.

We present a method for atomically precise nanocluster synthesis. As an illustration, we introduced the reducing-ligand induction combined method and synthesized a novel nanocluster, which was determined to be Au (SCH Ph- Bu) with the same number of gold atoms as existing Au (SR) nanoclusters but different ligands (hetero-composition-homo-size). Compared with the latter, the former has distinct properties and structures.

Traceless Removal of Two Kernel Atoms in a Gold Nanocluster and Its Impact on Photoluminescence.

Removing or adding kernel atoms of metal nanoclusters (NCs) without leaving a trace is a substantial challenge because the kernel atoms are inside and covered by the outer staples. However, such kernel tuning is very important for improving the properties and acquiring an in-depth understanding of the kernel-property correlation. Photoluminescence (PL) is one of the most intriguing characteristics of metal NCs but has not been well understood until now.

Distance makes a difference in crystalline photoluminescence.

Crystallization-induced photoluminescence weakening was recently revealed in ultrasmall metal nanoparticles. However, the fundamentals of the phenomenon are not understood yet. By obtaining conformational isomer crystals of gold nanoclusters, we investigate crystallization-induced photoluminescence weakening and reveal that the shortening of interparticle distance decreases photoluminescence, which is further supported by high-pressure photoluminescence experiments.

A Dual Purpose Strategy to Endow Gold Nanoclusters with Both Catalysis Activity and Water Solubility.

Gold nanoclusters have attracted extensive interest for catalysis applications in recent years due to their ultrasmall sizes and well-defined compositions and structures. However, at least two challenges exist in this emerging field. First, the steric hindrance of the ligands inhibits the catalysis activity, and second, the mechanism underlying water-phase catalysis using gold nanoclusters is often ambiguous.

Kernel Homology in Gold Nanoclusters.

Homology is well known in organic chemistry; however, it has not yet been reported in nanochemistry. Herein, we introduce the concept of kernel homology to describe the phenomenon of metal nanoclusters sharing the same "functional group" in kernels with some similar properties. To illustrate this point, we synthesized two novel gold nanoclusters, Au (TBBT) and Au (TBBT) (TBBTH=4-tert-butylbenzenethiol), and solved their total structures by X-ray crystallography, which reveals that they have the same Au bi-icosahedron capped with a similar bottom cap (Au and Au , respectively) in the kernels.

Real-Time X-ray Imaging Reveals Interfacial Growth, Suppression, and Dissolution of Zinc Dendrites Dependent on Anions of Ionic Liquid Additives for Rechargeable Battery Applications.

The dynamic interfacial growth, suppression, and dissolution of zinc dendrites have been studied with the imidazolium ionic liquids (ILs) as additives on the basis of in situ synchrotron radiation X-ray imaging. The phase contrast difference of real-time images indicates that zinc dendrites are preferentially developed on the substrate surface in the ammoniacal electrolytes. After adding imidazolium ILs, both nucleation overpotential and polarization extent increase in the order of additive-free < EMI-Cl < EMI-PF < EMI-TFSA < EMI-DCA.