Search

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, Au52(PET)32 and Au66(PET)38 (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 Au52(PET)32 to Au66(PET)38, we predicted six more novel nanoclusters. The concurrent synthesis provides rational comparison of the two nanoclusters on the stability, absorption, emission and photothermy, and reveals the aspect ratio‐related properties. An interesting finding is that the two nanoclusters exhibit concomitant PT and PL under 785 nm light irradiation, and the PT and PL are in balance, which was explained by the qualitative evaluation of the radiative and non‐radiative rates. The ligand effects on PT and PL were also investigated. [ABSTRACT FROM AUTHOR]

Atomically precise ~1‐nm Pt nanoparticles (nanoclusters, NCs) with ambient stability are important in fundamental research and exhibit diverse practical applications (catalysis, biomedicine, etc.). However, synthesizing such materials is challenging. Herein, by employing the mixture ligand protecting strategy, we successfully synthesized the largest organic‐ligand‐protected (~1‐nm) Pt23 NCs precisely characterized with mass spectrometry and single‐crystal X‐ray diffraction analyses. Interestingly, natural population analysis and Bader charge calculation indicate an alternate, varying charge ‐layer distribution in the sandwich‐like Pt23 NC kernel. Pt23 NCs can catalyze the oxygen reduction reaction under acidic conditions without requiring calcination and other treatments, and the resulting specific and mass activities without further treatment are sevenfold and eightfold higher than those observed for commercial Pt/C catalysts, respectively. Density functional theory and d‐band center calculations interpret the high activity. Furthermore, Pt23 NCs exhibit a photothermal conversion efficiency of 68.4 % under 532‐nm laser irradiation and can be used at least for six cycles, thus demonstrating great potential for practical applications. [ABSTRACT FROM AUTHOR]

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 Pd8 unit was found in the nanocluster, interacting with two syn PPh units through nonmetal‐to‐metal ‐ring coordination. The unexpected coordination, which is distinctly different from the typical organoring‐to‐metal coordination in half‐sandwich‐type organometallic compounds, contributes to the ambient stability of the as‐obtained single‐atom‐layered nanocluster as revealed through theoretical and experimental analyses. Furthermore, quantum chemical calculations revealed dominant electron transition along the horizontal x‐direction of the Pd8 plane, indicating high photothermal conversion efficiency (PCE) of the nanocluster, which was verified by the experimental PCE of 73.3 %. Therefore, this study unveils the birth of a novel type of compound and the finding of the unusual nonmetal‐to‐metal ‐ring coordination and has important implications for future syntheses, structures, properties, and structure–property correlations of single‐atom‐layered metal‐based materials. [ABSTRACT FROM AUTHOR]

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. In a freshly synthesized Au52(CHT)28 (CHT=S‐c−C6H11) nanocluster, the lattice distance of the (110) facet is found to be compressed from 4.51 to 3.58 Å at the near end. However, the lattice distances of the (111) and (100) facets show no change in different positions. The lattice‐compressed nanocluster exhibits superior electrocatalytic activity for the CO2 reduction reaction (CO2RR) compared to that exhibited by the same‐sized Au52(TBBT)32 (TBBT=4‐tert‐butyl‐benzenethiolate) nanocluster and larger Au nanocrystals without lattice variation, indicating that lattice tuning is an efficient method for tailoring the properties of metal nanoclusters. Further theoretical calculations explain the high CO2RR performance of the lattice‐compressed Au52(CHT)28 and provide a correlation between its structure and catalytic activity. [ABSTRACT FROM AUTHOR]

This article, published in Angewandte Chemie, discusses the discovery of the largest organic-ligand-protected Pt nanoclusters with atomic precision. The researchers found that these Pt23 nanoclusters exhibited superior catalytic activity for the oxygen reduction reaction under acidic conditions compared to commercial Pt/C catalysts, without the need for additional treatments. Additionally, the nanoclusters demonstrated excellent photothermal conversion efficiency, suggesting potential applications in various fields. The article also briefly mentions other research topics, including the synthesis of sulfur-containing polymers and the development of naphthalene diimide anolytes for neutral flow batteries. [Extracted from the article]

Metal nanoclusters have recently attracted considerable attention, not only because of their special size range but also because of their well‐defined compositions and structures. However, subtly tailoring the compositions and structures of metal nanoclusters for potential applications remains challenging. Now, a two‐phase anti‐galvanic reduction (AGR) method is presented for precisely tailoring Au44(TBBT)28 to produce Au47Cd2(TBBT)31 nanoclusters with a hard‐sphere random close‐packed structure, exhibiting Faradaic efficiencies of up to 96 % at −0.57 V for the electrocatalytic reduction of CO2 to CO. [ABSTRACT FROM AUTHOR]

Kernel atoms of Au nanoclusters are packed layer‐by‐layer along the [001] direction with every full (001) monolayer composed of 8 Au atoms (Au8 unit) in nanoclusters with formula of Au8n+4(TBBT)4n+8 (n is the number of Au8 units; TBBTH=4‐tert‐butylbenzenelthiol). It is unclear whether the kernel atoms can be stacked in a defective‐layer way along the [001] direction during growth of the series of nanoclusters and how the kernel layer number affects properties. Now, a nanocluster is synthesized that is precisely characterized by mass spectrometry and single‐crystal X‐ray crystallography, revealing a layer stacking mode in which a half monolayer composed of 4 atoms (Au4 unit) is stacked on the full monolayer along the [001] direction. The size and the odevity of the kernel layer number influence the properties (polarity, photoluminescence) of gold nanoclusters. The obtained nanocluster extends the previous formula from Au8n+4(TBBT)4n+8 to Au4n+4(TBBT)2n+8 (n is the number of Au4 units). [ABSTRACT FROM AUTHOR]

An assembly strategy for metal nanoclusters using electrostatic interactions with weak interactions, such as C−H⋅⋅⋅π and π⋅⋅⋅π interactions in which cationic [Ag26Au(2‐EBT)18(PPh3)6]+ and anionic [Ag24Au(2‐EBT)18]− nanoclusters gather and assemble in an unusual alternating array stacking structure is presented. [Ag26Au(2‐EBT)18(PPh3)6]+ [Ag24Au(2‐EBT)18]− is a new compound type, a double nanocluster ion compound (DNIC). A single nanocluster ion compound (SNIC) [PPh4]+ [Ag24Au(2‐EBT)18]− was also synthesized, having a k‐vector‐differential crystallographic arrangement. [PPh4]+ [Ag24Au(2,4‐DMBT)18]− adopts a different assembly mode from both [Ag26Au(2‐EBT)18(PPh3)6]+ [Ag24Au(2‐EBT)18]− and [PPh4]+ [Ag24Au(2‐EBT)18]−. Thus, the striking packing differences of [Ag26Au(2‐EBT)18(PPh3)6]+ [Ag24Au(2‐EBT)18]−, [PPh4]+ [Ag24Au(2‐EBT)18]− and the existing [PPh4]+ [Ag24Au(2,4‐DMBT)18]− from each other indicate the notable influence of ligands and counterions on the self‐assembly of nanoclusters. [ABSTRACT FROM AUTHOR]

Although face-centered cubic (fcc), body-centered cubic (bcc), hexagonal close-packed (hcp), and other structured gold nanoclusters have been reported, it was unclear whether gold nanoclusters with mix-packed (fcc and non-fcc) kernels exist, and the correlation between kernel packing and the properties of gold nanoclusters is unknown. A Au49(2,4-DMBT)27 nanocluster with a shell electron count of 22 has now been been synthesized and structurally resolved by single-crystal X-ray crystallography, which revealed that Au49(2,4-DMBT)27 contains a unique Au34 kernel consisting of one quasi-fcc-structured Au21 and one non-fcc-structured Au13 unit (where 2,4-DMBTH=2,4-dimethylbenzenethiol). Further experiments revealed that the kernel packing greatly influences the electrochemical gap (EG) and the fcc structure has a larger EG than the investigated non-fcc structure. [ABSTRACT FROM AUTHOR]