Synthesis and functionalities of FeSn12 superatom prepared by single atom introduction with a dendrimer template.

Superatoms are promising as new building block materials that can be designed by precise controlling of the constituent atoms. Stannaspherene (Sn12 2-) is a rigid cage-like cluster with icosahedral symmetry, for which one-atom encapsulation was theoretically expected and detected in the gas phase. Here, a single-atom introduction method into stannaspherene using a dendrimer template with polyvinylpyrrolidone (PVP) protection is demonstrated. This advanced solution-phase synthesis allows not only the selective doping of one atom into the cluster cage, but also enable further detail characterization of optical and magnetic properties that were not possible in the gas-phase synthesis. In other words, this liquid-phase synthesis method has enabled the adaptation of detailed analytical methods. In this study, FeSn12 was synthesized and characterized, revealing that a single Fe atom introduction in the Sn12 2- cage result in the appearance of near-infrared emission and enhancement in the magnetism.

Ultra-small Mo-Pt subnanoparticles enable CO2 hydrogenation at room temperature and atmospheric pressure.

We present a partially-oxidised bimetallic Mo-Pt subnanoparticle (Mo4Pt8Ox) enabling thermally-driven CO2 hydrogenation to CO at room temperature and atmospheric pressure. A mechanistic study explained the full catalytic cycle of the reaction from CO2 activation to catalyst reactivation. DFT calculations revealed that alloying with Mo lowers the activation barrier by weakening the CO adsorption. This finding could be a first step for low-energy CO2 conversion.

Alloying at a Subnanoscale Maximizes the Synergistic Effect on the Electrocatalytic Hydrogen Evolution.

Bonding dissimilar elements to provide synergistic effects is an effective way to improve the performance of metal catalysts. However, as the properties become more dissimilar, achieving synergistic effects effectively becomes more difficult due to phase separation. Here we describe a comprehensive study on how subnanoscale alloying is always effective for inter-elemental synergy. Thirty-six combinations of both bimetallic subnanoparticles (SNPs) and nanoparticles (NPs) were studied systematically using atomic-resolution imaging and catalyst benchmarking based on the hydrogen evolution reaction (HER). Results revealed that SNPs always produce greater synergistic effects than NPs, the greatest synergistic effect was found for the combination of Pt and Zr. The atomic-scale miscibility and the associated modulation of electronic states at the subnanoscale were much different from those at the nanoscale, which was observed by annular-dark-field scanning transmission electron microscopy (ADF-STEM) and X-ray photoelectron spectroscopy (XPS), respectively.

Controlled Synthesis of Au25 Superatom Using a Dendrimer Template.

Superatoms are promising materials for their potential in elemental substitution and as new building blocks. Thus far, various synthesis methods of thiol-protected Au clusters including an Au25 superatom have been investigated. However, previously reported methods were mainly depending on the thermodynamic stability of the aimed clusters. In this report, a synthesis method for thiol-protected Au clusters using a dendrimers template is proposed. In this method, the number of Au atoms was controlled by the stepwise complexation feature of a phenylazomethine dendrimer. Therefore, synthesis speed was increased compared with the case without the dendrimer template. Hybridization for the Au25 superatoms was also achieved using the complexation control of metals.

Dynamic hetero-metallic bondings visualized by sequential atom imaging.

Traditionally, chemistry has been developed to obtain thermodynamically stable and isolable compounds such as molecules and solids by chemical reactions. However, recent developments in computational chemistry have placed increased importance on studying the dynamic assembly and disassembly of atoms and molecules formed in situ. This study directly visualizes the formation and dissociation dynamics of labile dimers and trimers at atomic resolution with elemental identification. The video recordings of many homo- and hetero-metallic dimers are carried out by combining scanning transmission electron microscopy (STEM) with elemental identification based on the Z-contrast principle. Even short-lived molecules with low probability of existence such as AuAg, AgCu, and AuAgCu are directly visualized as a result of identifying moving atoms at low electron doses.

Synthesis and magnetic properties of sub-nanosized iron carbides on a carbon support.

Iron carbide clusters with near-sub-nanometer size have been synthesized by employing a tetraphenylmethane-cored phenylazomethine dendrimer generation 4 (TPM-DPAG4) as a molecular template. Magnetic measurements reveal that these iron carbide clusters exhibit a magnetization-field hysteresis loop at 300 K. The data indicate that these iron carbide clusters are ferromagnets at room temperature.

Unique Functions and Applications of Rigid Dendrimers Featuring Radial Aromatic Chains.

Dendrimers, which are highly branched polymers and regarded as huge single molecules, are interesting substances from the aspect of not only polymer chemistry but also molecular chemistry. Various applications in materials science and life science have been investigated by taking advantage of the radially layered structures and intramolecular nanospaces of dendrimers. Most dendrimers have flexible structures that originate from their organic chains which contain many sp3-type atoms, while relatively rigid dendrimers composed only of sp2-type atoms have rarely been reported. It has been recently clarified that such rigid dendrimers exhibit a specific aromatic property not found in other materials. Dendritic phenylazomethines (DPAs), as one of the rigid dendrimers, have only sp2-type C and N atoms and possess a radially branched π-conjugation system in their own macromolecular chains. Such geometric and electronic structures heighten the electron density at the core of the dendrimer and induce an intramolecular potential gradient, which affords unique reactivities that lead to extraordinary functions. This unique property of the rigid dendrimers can be regarded as a new atypical electronic state based on radial aromatic chains not found in conventional aromatic compounds containing spherical aromaticity, Möbius aromaticity, metal aromaticity, and conductive polymers. Therefore, this as-yet-unknown characteristic is expected to contribute to the further development of fundamental and materials chemistry.In this Account, we highlight the rigid DPA dendrimers and their peculiar atomically precise and selective assembly behaviors that originate from the radial aromatic chains. One of the most noteworthy attainments based on the radial aromatic chains is the precise synthesis of a multimetallic multinuclear complex of a dendrimer containing a total of 13 elements. Next, we describe the electrochemical and catalytic functionalization of such multinuclear dendrimer complexes and the construction of supramolecular nanoarchitectures by the polymerization of DPAs. These complexes exhibit encapsulation-release switching of guests and additive-free catalytic ability similar to proteins and enzymes. Such selective and accurate control of the intramolecular assembly of guests and the intermolecular arrangement of hosts realized by the radial aromatic chains of dendrimers will enable supramolecular chemistry and biochemistry to be linked from a new aspect. In addition, the multimetallic multinuclear complexes of dendrimers afford a novel approach to precisely synthesize sub-nanoparticles with ultrasmall particle sizes (1 nm) that have been technically difficult to obtain by conventional nanotechnology. We discuss the method for the synthesis of these sub-nanoparticles with well-controlled atomicity and composition using DPA complexes as a template and recent advances to reveal their specific physical and chemical properties. These results suggest that the unique electronic states induced in such radial aromatics could play an important role in the development of next-generation chemistry.

Metal atom-guided conformational analysis of single polynuclear coordination molecules.

Microscopic observation of single molecules is a rapidly expanding field in chemistry and differs from conventional characterization techniques that require a large number of molecules. One of such form of single-molecule microscopy is high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), which is especially suitable for coordination compounds because of its atomic number-dependent contrast. However, to date, single-molecule observations using HAADF-STEM has limited to simple planar molecules. In the present study, we demonstrate a direct structural investigation of nonplanar dendronized polynuclear Ir complexes with subnanometer resolution using Ir as an atomic label. Decreasing the electron dose to the dendrimer complexes is critical for the single-molecule observation. A comparison with simulated STEM images of conformational isomers is performed to determine the most plausible conformation. Our results enlarge the potential of electron microscopic observation to realize structural analysis of coordination macromolecules, which has been impossible with conventional methods.

Low-Temperature H2 Reduction of Copper Oxide Subnanoparticles.

Invited for the cover of this issue is Kimihisa Yamamoto and co-workers at Tokyo Institute of Technology and International Christian University. The image depicts enhanced reactivity of the copper oxide subnanoparticles under low-temperature conditions. Read the full text of the article at 10.1002/chem.202100508.

Low-Temperature H2 Reduction of Copper Oxide Subnanoparticles.

Subnanoparticles (SNPs) with sizes of approximately 1 nm are attractive for enhancing the catalytic performance of transition metals and their oxides. Such SNPs are of particular interest as redox-active catalysts in selective oxidation reactions. However, the electronic states and oxophilicity of copper oxide SNPs are still a subject of debate in terms of their redox properties during oxidation reactions for hydrocarbons. In this work, in situ X-ray absorption fine structure (XAFS) measurements of Cu28 Ox SNPs, which were prepared by using a dendritic phenylazomethine template, during temperature-programmed reduction (TPR) with H2 achieved lowering of the temperature (T50 =138 °C) reported thus far for the CuII →CuI reduction reaction because of Cu-O bond elongation in the ultrasmall copper oxide particles.

Highly Dispersed Molybdenum Oxycarbide Clusters Supported on Multilayer Graphene for the Selective Reduction of Carbon Dioxide.

Molybdenum oxycarbide clusters are novel nanomaterials that exhibit attractive catalytic activity; however, the methods for their production are currently very restrictive. This work represents a new strategy for the creation of near-subnanometer size molybdenum oxycarbide clusters on multilayer graphene. To adsorb Mo-based polyoxometalates of the type [PMo12 O40 ]3- as a precursor for Mo oxycarbide clusters, the novel tripodal-phenyl cation N,N,N-tri(4-phenylbutyl)-N-methylammonium ([TPBMA]+ ) is synthesized. [TPBMA]+ exhibits superior adsorption on multilayer graphene compared to commercially available cations such as tetrabutylammonium ([nBu4 N]+ ) and tetraphenylphosphonium ([PPh4 ]+ ). Using [TPBMA]+ as an anchor, highly dispersed precursor clusters (diameter: 1.0 ± 0.2 nm) supported on multilayer graphene are obtained, as confirmed by high-resolution scanning transmission electron microscopy. Remarkably, this new material achieves the catalytic reduction of CO2 to selectively produce CO (≈99.9%) via the reverse water-gas-shift reaction, by applying carbothermal hydrogen reduction to generate Mo oxycarbide clusters in situ.

Modern cluster design based on experiment and theory.

For decades, chemists have explored cluster compounds according to theoretical models that have proved too simplistic to accurately predict cluster properties, stabilities and functions. By incorporating molecular symmetry into existing cluster models, we can better study real polyatomic molecules and have new guidelines for their design. This symmetry-adapted cluster model allows us to discover substances that shatter the conventional notion of clusters. Theoretical predictors will point to the viability of new clusters, whose syntheses can be realized with parallel advances in experimental methods. This Perspective describes these modern experimental and theoretical strategies for cluster design and how they may give rise to new fields in cluster chemistry.

Silver in the Center Enhances Room-Temperature Phosphorescence of a Platinum Sub-nanocluster by 18 Times.

There has been controversy surrounding the roles of the metal core (metal-metal interaction) and the shell (metal-ligand interaction) in photoluminescence of ligand-protected metal nanoclusters. We have discovered aggregation-induced room-temperature phosphorescence of a platinum-thiolate complex and its silver ion inclusion complex (a silver-doped platinum sub-nanocluster). The inclusion of silver ion boosted the photoluminescent quantum yield by 18 times. Photophysical measurements indicate that the rate of nonradiative decay was slower for the silver-doped platinum sub-nanocluster. DFT calculations showed that the LUMO, which had the main contribution from Ag s-orbital and Pt d-orbitals, played a critical role in suppressing the structural distortion at the excited state. This work will hopefully stimulate more research on designing strategies based on molecular orbitals of atomicity-precise luminescent multimetallic nanoclusters.

Metallic Tungsten Nanoparticles That Exhibit an Electronic State Like Carbides during the Carbothermal Reduction of WCl6 by Hydrogen.

Carbothermal hydrogen reduction (CHR) is a unique dry chemical process used to fabricate metals and carbides on carbon supports. In this study, a stepwise CHR of WCl6 on a graphite support is demonstrated for the first time. Powder X-ray diffraction studies revealed that, at 773 K, metallic tungsten nanoparticles are produced, whereas, at 1073 K, the metastable W2C phase is generated rather than the thermodynamically stable WC phase. X-ray photoelectron spectroscopy and X-ray absorption near edge structure studies showed that the chemical state of the W nanoparticles simultaneously exhibits metallic W(∼0) and carbide W(δ+) character. The obtained results suggest that, although electronic interactions exist between the metallic W atoms and the graphite support, the body-centered cubic structure of the metallic tungsten is maintained, confirmed by the extended X-ray absorption fine structure. In addition, high-resolution scanning transmission electron microscopy observations revealed that the W nanoparticles exhibit a thin flattened shape on the support. These results support the notion that the mechanism for the formation of the W nanoparticles during the CHR is influenced by the electronic interactions between the W nanoparticles and the graphite support. Our work thus suggests that the combination of early-transition-metal atoms and carbon-based supports would afford modulatable electronic systems though the electronic interactions.

Subnano-transformation of molybdenum carbide to oxycarbide.

Ultrasmall particles exhibit structures and/or properties that are different from those of the corresponding bulk materials; in this context especially ultrasmall precious-metal particles have been extensively investigated. In this study, we targeted the transition base-metal Mo and succeeded in systematically producing Mo oxycarbide/carbide particles with diameters of 1.7 ± 0.7, 1.4 ± 0.5, 1.3 ± 0.4, 1.2 ± 0.3, 1.0 ± 0.3, and 0.8 ± 0.2 nm on a carbon support using the carbothermal hydrogen reduction method at 773 K and a diphenylazomethine-type dendrimer as a template. The formation and properties of the particles were confirmed using X-ray photoelectron spectroscopy, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images, and X-ray absorption fine structure (XAFS) studies. We found that Mo particles with a diameter of 1.3 nm or greater formed carbides such as ß'-Mo2C, whereas smaller particles formed oxycarbides, indicating a size-dependent transformation in the phase or composition of the particles. Thus, this work demonstrated a new concept, subnano-transformation, which would be a new class of phase transformation based on the concept of the size dependence in such an ultrasmall scale. In addition, the movement of Mo atoms within a cluster and on the fringes of a nanoparticle was also demonstrated during continuous time-course high-resolution HAADF-STEM observation.

Superatomic Gallium Clusters in Dendrimers: Unique Rigidity and Reactivity Depending on their Atomicity.

Superatoms have been investigated due to their possible substitution for other elements. The solution-phase synthesis of superatoms has attracted attention to realize the availability of superatoms. However, the previous approach is basically limited to the formation of a single cluster. Here, superatoms are investigated and the number of valence electrons in these superatoms is changed by designing the number of gallium atoms present. Based on the dendrimer template method, clusters consisting of 3, 12, 13, and other numbers of atoms have been synthesized. The halogen-like superatomic nature of Ga13 is structurally and electrochemically observed as completely different to the other clusters. The gallium clusters of 13 and 3 atoms, which can fill the 2P and 1P superatomic orbitals, respectively, exhibit different reactivities. The 3-atom gallium cluster is suggested as being reduced to Ga3 H2 - due to the lower shift of energy levels in the unoccupied orbitals. The results for these gallium clusters provide candidates for superatoms.

A useful preparation of ultrasmall iron oxide particles by using arc plasma deposition.

Ultrasmall particles, different from the larger size nanoparticles, have recently attracted significant attention in the scientific community in nanotechnology for catalytic, electronic and optical applications; however, their magnetic properties remain unexplored due to the difficult structural analysis. A challenging issue is to develop a preparation method for iron oxide particles (IOPs) with fine size control, and to determine the dependence of magnetic properties on the morphology and crystallinity of the magnetic particles. However, synthetic approaches to obtain IOPs, regarded as one of the new fields of magnetic nanoparticles, have been significantly limited. This article reported a developed synthetic method to prepare IOPs on carbon supports using pulsed arc plasma deposition (APD) in flowing oxygen gas, which clarified the finely-controlled formation of IOPs on graphene nanosheets. Structural characterization of the IOPs revealed the formation of crystalline γ-Fe2O3 ultrasmall particles with oxygen deficiency. The pulsed APD method for IOPs is the first simple and convenient technique to not only prevent significant aggregation and contamination by organic compounds and avoid the need for thermal pretreatment, but also provide uniform crystalline nano-order particles.

New Horizon of Nanoparticle and Cluster Catalysis with Dendrimers.

Among various approaches synthesizing metal nanoparticles and tiny clusters, a template method using dendrimers has significant advantages over other chemical approaches with respect to their synthetic precision and the scalability. A dendrimer of polydentate ligands assembles metal ions or salts into the interior allowing production of metal nanoparticles in the dendrimer. The dendrimer-encapsulated nanoparticles (DENs) exhibit unique and remarkable catalytic properties depending on the size and elemental formula. Recent advances in dendrimer chemistry even enabled the atom precise synthesis of subnanometer metal clusters that have been impossible to prepare by wet chemical methods. In addition, not only for the synthesis of metal nanoparticles and clusters, the dendrimer itself can also provide the modulation of activity and selectivity in the catalysis. In this review, we summarized the most relevant research in which the dendrimer was employed as the template, modulator, or stabilizer for nanoparticle synthesis for catalytic applications.

Composition-defined nanosized assemblies that contain heterometallic early 4d/5d-transition-metals.

The controlled assembly of early transition metals remains a challenging research target, especially with respect to the generation of heterometallic molecules and nanomaterials. In this study, metal chlorides of the early 4d/5d-transition-metals, i.e., ZrCl4, NbCl5, MoCl5, HfCl4, TaCl5, and WCl6, were stoichiometrically introduced into a tetraphenylmethane-core dendritic-phenylazomethine generation 4 dendrimer in the presence of an optimal amount of organic ligands such as pyridine and 3-chloropyridine. The coordinative interactions between the metal chlorides and the imines in the dendrimers indicated a positive correlation for the Lewis acidity of the metals. Moreover, it was clearly demonstrated for the first time that heterometallic assemblies of defined composition contain four kinds of early 4d/5d-transition-metals, such as TaV, NbV, MoV, and ZrIV, which was confirmed by UV-vis titration, XPS, and HAADF-STEM/EDS measurements. The results of this study should provide access to new routes to produce nanomaterials composed of heterometallic early 4d/5d-transition metals.

Isomerizations of a Pt4 cluster revealed by spatiotemporal microscopic analysis.

We now report the first direct observation of the fluxional nature in which the four-atomic platinum cluster (Pt4) randomly walks through several isomers. Time-lapse analysis by a Cs-corrected transmission electron microscope allowed us to acquire the atomic coordinates at a sub-angstrom space resolution and 0.2 s time resolution for each cluster isomer. The analysis revealed that the isomerization follows a simple first-order kinetic model.