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Selective oxidative etching is one of the most effective ways to prepare hollow nanostructures and nanocrystals with specific exposed facets. The mechanism of selective etching in noble metal nanostructures mainly relies on the different reactivity of metal components and the distinct surface energy of multimetallic nanostructures. Recently, phase engineering of nanomaterials (PEN) offers new opportunities for the preparation of unique heterostructures, including heterophase nanostructures. However, the synthesis of hollow multimetallic nanostructures based on crystal‐phase‐selective etching has been rarely studied. Here, a crystal‐phase‐selective etching method is reported to selectively etch the unconventional 4H and 2H phases in the heterophase Au nanostructures. Due to the coating of Pt‐based alloy and the crystal‐phase‐selective etching of 4H‐Au in 4H/face‐centered cubic (fcc) Au nanowires, the well‐defined ladder‐like Au@PtAg nanoframes are prepared. In addition, the 2H‐Au in the fcc‐2H‐fcc Au nanorods and 2H/fcc Au nanosheets can also be selectively etched using the same method. As a proof‐of‐concept application, the ladder‐like Au@PtAg nanoframes are used for the electrocatalytic hydrogen evolution reaction (HER) in acidic media, showing excellent performance that is comparable to the commercial Pt/C catalyst. [ABSTRACT FROM AUTHOR]

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]

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]

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]

Improving the catalytic activity of non-noble metal single atom catalysts (SACs) has attracted considerable attention in materials science. Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity, it often involves in-plane modulation and requires high temperatures. Herein, we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co–S bond anchored onto graphitic carbon nitride (C3N4) at room temperature (RT). Each Co atom is bonded to four N atoms and one S atom (Co-(N, S)/C3N4). Owing to the greater electronegativity of S in the Co–S bond, the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level. Consequently, when employed for the photocatalytic hydrogen evolution reaction, the adsorption energy of intermediate hydrogen (H*) on the Co atoms is remarkably low. In the presence of the Co-(N, S)/C3N4 SACs, the hydrogen evolution rates reach up to 10 mmol/(gh), which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C3N4 and noble platinum nanoparticles (PtNPs)/C3N4 catalysts, respectively. Attributed to the tailorable axial Co-S bond in the SAC, the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions. This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic 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]

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]

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]

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≈0.9 nm and length≈0.25 nm) by introducing the furfuryl mercaptan ligand (FUR) and the alloying strategy. Interestingly, the kernel consists of a centered silver atom and two planar Ag10 pentacle units with completely mirrored symmetry after a rotation of 36 degrees. The two Ag10 pentacles and some extended structures show an unreported golden ratio geometry, and the two inner five‐membered rings and the centered Ag atom form an unanticipated full‐metal ferrocene‐like structure. The featured kernel structure causes the dominant radial direction transition of excitation electrons, as determined via time‐dependent density functional theory calculations, which affords the protruding absorption at 612 nm and contributes to the promising photothermal conversion efficiency of 67.6 % of the as‐obtained nanocluster, having important implications for structure‐property correlation and the development of nanocluser‐based photothermal materials. [ABSTRACT FROM AUTHOR]

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≈0.9 nm and length≈0.25 nm) by introducing the furfuryl mercaptan ligand (FUR) and the alloying strategy. Interestingly, the kernel consists of a centered silver atom and two planar Ag10 pentacle units with completely mirrored symmetry after a rotation of 36 degrees. The two Ag10 pentacles and some extended structures show an unreported golden ratio geometry, and the two inner five‐membered rings and the centered Ag atom form an unanticipated full‐metal ferrocene‐like structure. The featured kernel structure causes the dominant radial direction transition of excitation electrons, as determined via time‐dependent density functional theory calculations, which affords the protruding absorption at 612 nm and contributes to the promising photothermal conversion efficiency of 67.6 % of the as‐obtained nanocluster, having important implications for structure‐property correlation and the development of nanocluser‐based photothermal materials. [ABSTRACT FROM AUTHOR]

A recent research article in the journal Angewandte Chemie International Edition discusses the discovery of the largest organic-ligand-protected Pt nanoclusters with atomic precision. These nanoclusters, obtained through a mixture ligand protecting strategy, demonstrate superior catalytic activity for the oxygen reduction reaction under acidic conditions compared to commercial Pt/C catalysts. Additionally, the nanoclusters exhibit excellent photothermal conversion efficiency, suggesting potential applications in various fields. Another research article in the same journal explores the synthesis of sulfur-containing polymers with high melting points through the copolymerization of phenylisothiocyanate and oxetane. Lastly, a hydrothermal method for synthesizing naphthalene diimide anolytes for neutral flow batteries is reported, which enhances their solubility and stability. [Extracted from the article]

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]

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. Inspired by these challenges/questions, we conducted this study and, for the first time, achieved the traceless removal of two kernel atoms in a gold nanocluster by applying a simple thermal treatment and revealed its impact on PL. Further, we demonstrated that the kernel Au‐Au bond length can be an indicator for a comparison of the PL or kernel charge state between nanoclusters with similar kernel structures and sizes. [ABSTRACT FROM AUTHOR]

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. Inspired by these challenges/questions, we conducted this study and, for the first time, achieved the traceless removal of two kernel atoms in a gold nanocluster by applying a simple thermal treatment and revealed its impact on PL. Further, we demonstrated that the kernel Au‐Au bond length can be an indicator for a comparison of the PL or kernel charge state between nanoclusters with similar kernel structures and sizes. [ABSTRACT FROM AUTHOR]

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]

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]

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]

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]

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Structural isomerism allows the correlation between structures and properties to be investigated. Unfortunately, the structural isomers of metal nanoparticles are rare and genuine structural isomerism with distinctly different kernel atom packing (e.g. face‐centered cubic (fcc) vs. non‐fcc) has not been reported until now. Herein we introduce a novel ion‐induction method to synthesize a unique gold nanocluster with a twist mirror symmetry structure. The as‐synthesized nanocluster has the same composition but different kernel atom packing to an existing gold nanocluster Au42(TBBT)26 (TBBT=4‐tert‐butylbenzenethiolate). The fcc‐structured Au42(TBBT)26 nanocluster shows more enhanced photoluminescence than the non‐fcc‐structured Au42(TBBT)26 nanocluster, indicating that the fcc‐structure is more beneficial for emission than the non‐fcc structure. This idea was supported by comparison of the emission intensity of another three pairs of gold nanoclusters with similar compositions and sizes but with different kernel atom packings (fcc vs. non‐fcc). Cores and effect: A so‐called "ion‐induction" method gives a unique gold nanocluster with a twist mirror symmetry structure. The as‐synthesized nanocluster has the same composition but a different packing of the core kernel atoms (fcc vs. non‐fcc) with an existing gold nanocluster Au42(TBBT)26 (TBBT=4‐tert‐butylbenzenethiolate), and shows photoluminescence that is dependent on the kernel‐atom packing. [ABSTRACT FROM AUTHOR]

This article, published in Angewandte Chemie International Edition, discusses various research articles in the field of chemistry. One article by Jun Li, Zhikun Wu, and their colleagues explores the unexpected coordination of nonmetal-to-metal aromatic ring coordination in single-atom-layered Pd nanoclusters, which provides exceptional stability and promising photothermal conversion efficiency. Another article by Jun Xu, Feng Deng, and their team investigates micro-hydrophobic effects in benzene methylation over ZSM-5 zeolite using solid-state NMR and theoretical simulations. Additionally, Fengchao Cui, Heng-Guo Wang, Guangshan Zhu, and their co-workers construct a redox-active hydrogen-bonded organic framework for use as a cathode material in aqueous zinc-ion batteries. Lastly, Changliang Ren and his team present a class of non-covalently stapled H+/Cl- ion channels that can be activated by visible light. [Extracted from the article]

This article, published in Angewandte Chemie, discusses several research articles on different topics in chemistry. One article by Jun Li, Zhikun Wu, and their colleagues explores the coordination of nonmetal-to-metal aromatic rings in single-atom-layered Pd nanoclusters, which results in exceptional stability and promising photothermal conversion efficiency. Another article by Jun Xu, Feng Deng, and their team investigates micro-hydrophobic effects in benzene methylation over ZSM-5 zeolite using solid-state NMR and theoretical simulations. Additionally, Fengchao Cui, Heng-Guo Wang, Guangshan Zhu, and their co-workers construct a redox-active hydrogen-bonded organic framework for use as a cathode material in aqueous zinc-ion batteries. Lastly, Changliang Ren and his team present a class of non-covalently stapled H+/Cl- ion channels that can be activated by visible light. [Extracted from the article]

Copyright of Angewandte Chemie is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

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, Au44(TBBT)26 and Au48(TBBT)28 (TBBTH=4‐tert‐butylbenzenethiol), and solved their total structures by X‐ray crystallography, which reveals that they have the same Au23 bi‐icosahedron capped with a similar bottom cap (Au6 and Au8, respectively) in the kernels. The two novel gold nanoclusters, together with the existing Au38(PET)24 nanocluster (PETH=phenylethanethiol), have the same "functional group"—Au23—in their kernels and have some similar properties (e.g. electrochemical properties); therefore, they are comparable to the homologues in organic chemistry. Two gold nanoclusters, Au44(TBBT)26 and Au48(TBBT)28 (TBBTH=4‐tert‐butylbenzenethiol), were synthesized and their total structures solved. The two gold nanoclusters, together with the existing Au38(PET)24 nanocluster (PETH=phenylethanethiol), have the same "functional group" (Au23) in their kernels and have some similar (electrochemical) properties; therefore, they are comparable to the homologues in organic chemistry. [ABSTRACT FROM AUTHOR]

Abstract: The emergence of thiolated metal nanoclusters provides opportunities to identify significant and unprecedented phenomena because they are at quantum sizes and can be characterized with X‐ray crystallography. Recently silver nanoclusters have received extensive interest owing to their merits, such as low‐cost and rich properties. Herein, a thiolated silver nanocluster [Ag46S7(SPhMe2)24]NO3 (Ag46 for short) with a face‐centered cubic (fcc) structure was successfully synthesized and structurally resolved by X‐ray analysis. Most importantly, interstitial sulfur was found in the lattice void of Ag46 without lattice distortion or expansion, indicating that the classic theory of interstitial metal solid solutions might be not applicable at quantum size. Furthermore, unprecedented chemical bonds and unique structural features (such as asymmetrically coordinated μ4‐S) were found in Ag46 and might be related to the interstitial sulfur, which is supported by natural population analyses. [ABSTRACT FROM AUTHOR]

Abstract: The emergence of thiolated metal nanoclusters provides opportunities to identify significant and unprecedented phenomena because they are at quantum sizes and can be characterized with X‐ray crystallography. Recently silver nanoclusters have received extensive interest owing to their merits, such as low‐cost and rich properties. Herein, a thiolated silver nanocluster [Ag46S7(SPhMe2)24]NO3 (Ag46 for short) with a face‐centered cubic (fcc) structure was successfully synthesized and structurally resolved by X‐ray analysis. Most importantly, interstitial sulfur was found in the lattice void of Ag46 without lattice distortion or expansion, indicating that the classic theory of interstitial metal solid solutions might be not applicable at quantum size. Furthermore, unprecedented chemical bonds and unique structural features (such as asymmetrically coordinated μ4‐S) were found in Ag46 and might be related to the interstitial sulfur, which is supported by natural population analyses. [ABSTRACT FROM AUTHOR]

Keywords: AgCu Nanoclusters; Golden Ratio; Pentacle; Photothermal Conversion; Structure-Property Correlation EN AgCu Nanoclusters Golden Ratio Pentacle Photothermal Conversion Structure-Property Correlation 1 1 1 09/01/23 20230904 NES 230904 B Nanoclusters b . A silver-copper nanocluster with a golden ratio pentangle structure was prepared by Nan Yan, Zhikun Wu et al. in their Research Article (e202305604). AgCu Nanoclusters, Golden Ratio, Pentacle, Photothermal Conversion, Structure-Property Correlation. [Extracted from the article]

A silver-copper nanocluster with a golden ratio pentangle structure was prepared by Nan Yan, Zhikun Wu et al. in their Research Article (e202305604). Keywords: AgCu Nanoclusters; Golden Ratio; Pentacle; Photothermal Conversion; Structure-Property Correlation EN AgCu Nanoclusters Golden Ratio Pentacle Photothermal Conversion Structure-Property Correlation 1 1 1 08/31/23 20230904 NES 230904 B Nanoclusters b . AgCu Nanoclusters, Golden Ratio, Pentacle, Photothermal Conversion, Structure-Property Correlation. [Extracted from the article]

We report the size-dependent reactivity of phenylethanethiolated gold nanoparticles with acetic acid. Employing this reactivity, we synthesize a novel nanocluster Au38(PET)26 (PET: phenylethanethiolate), which is otherwise difficult to obtain and exhibits remarkably different photoluminescence and electrochemical properties compared with the well-known Au38(PET)24 nanoclusters. And the reaction process between Au38(PET)26 and acetic acid was probed by matrix-assisted laser desorption/ionization time of flight mass spectrometry. [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]

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]

Herein, we report the intriguing structure, optical absorption and electrochemical properties of the transition-sized Au92(TBBT)44 (Au92 for short, TBBT = 4-tert-butylbenzenethiolate) nanoparticle. An interesting observation is the 4H phase array of Au92 nanoparticles in the unit cells of single crystals. [ABSTRACT FROM AUTHOR]

The structural features that render gold nanoclusters intrinsically fluorescent are currently not well understood. To address this issue, highly fluorescent gold nanoclusters have to be synthesized, and their structures must be determined. We herein report the synthesis of three fluorescent Au24(SR)20 nanoclusters (R=C2H4Ph, CH2Ph, or CH2C6H4 tBu). According to UV/Vis/NIR, differential pulse voltammetry (DPV), and X-ray absorption fine structure (XAFS) analysis, these three nanoclusters adopt similar structures that feature a bi-tetrahedral Au8 kernel protected by four tetrameric Au4(SR)5 motifs. At least two structural features are responsible for the unusual fluorescence of the Au24(SR)20 nanoclusters: Two pairs of interlocked Au4(SR)5 staples reduce the vibration loss, and the interactions between the kernel and the thiolate motifs enhance electron transfer from the ligand to the kernel moiety through the Au−S bonds, thereby enhancing the fluorescence. This work provides some clarification of the structure-fluorescence relationship of such clusters. [ABSTRACT FROM AUTHOR]

The structural features that render gold nanoclusters intrinsically fluorescent are currently not well understood. To address this issue, highly fluorescent gold nanoclusters have to be synthesized, and their structures must be determined. We herein report the synthesis of three fluorescent Au24(SR)20 nanoclusters (R=C2H4Ph, CH2Ph, or CH2C6H4 tBu). According to UV/Vis/NIR, differential pulse voltammetry (DPV), and X-ray absorption fine structure (XAFS) analysis, these three nanoclusters adopt similar structures that feature a bi-tetrahedral Au8 kernel protected by four tetrameric Au4(SR)5 motifs. At least two structural features are responsible for the unusual fluorescence of the Au24(SR)20 nanoclusters: Two pairs of interlocked Au4(SR)5 staples reduce the vibration loss, and the interactions between the kernel and the thiolate motifs enhance electron transfer from the ligand to the kernel moiety through the Au−S bonds, thereby enhancing the fluorescence. This work provides some clarification of the structure-fluorescence relationship of such clusters. [ABSTRACT FROM AUTHOR]

Herein we report three important results of widespread interest, which are (1) the crystal structure of [Au24Pt(PET)18]0, (2) the crystal structure of [Au24Pd(PET)18]0 and (3) the main source of magnetism in [Au25(PET)18]0. [ABSTRACT FROM AUTHOR]

Thiolated silver nanoparticles have recently received extensive interests in terms of their syntheses, properties, and applications; however, their cytotoxicity has not been paid great attention. Some issues related to the cytotoxicity remained unresolved: What is the relationship between size and cytotoxicity? How to rapidly probe their cytotoxicity?, and so forth. In this work, differential pulse voltammetry (DPV) is, for the first time, introduced to rapidly and preliminarily evaluate the cytotoxicity of silver nanoparticles on the basis of the finding that the silver-ion signal intensity probed by DPV is positively correlated to the cytotoxicity of silver nanoparticles. It is found that the cytotoxicity of silver nanoparticles is size dependent in the investigated size range, that is, with increasing size, the cytotoxicity increases. Our work advances one step toward monitoring and understanding the cytotoxicity of thiolated silver nanoparticles. [ABSTRACT FROM AUTHOR]

Formic acid oxidation is an important electrocatalytic reaction in protonexchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCOO* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/activation towards improved electrocatalytic performance. [ABSTRACT FROM AUTHOR]

Controlling alloy nanoparticles with atomic monodispersity is challenging, and the recently revealed anti-galvanic reduction (AGR) provides a unique solution to this challenge. Herein we demonstrate that AGR is ion-precursor and ion-dose dependent, which offers novel strategies to tune the composition, structure and properties of nanoparticles by varying the ion-precursor and ion-dose in the AGR reaction. [ABSTRACT FROM AUTHOR]