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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.

ConspectusDendrimers, 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, Mobius 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.

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.

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. Theoretical models of clusters that account for molecular symmetry offer guidelines for their design. This Perspective describes the models and how we can synthesize the clusters thus designed.

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.

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.

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 β'-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.

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.

Dendrimers can provide unique reaction space for sub-nano sized materials. Recently, we have demonstrated a luminous bismuth dendrimer and the on/off switching by stepwisely assembled bismuth units in a phenylazomethine dendrimers. In addition, formation of bismuth clusters was also demonstrated by the reduction of the bismuth salts assembled in the dendrimer. In this study, we have revealed the atomicity dependency about the reduction and oxidation potentials of the assembled bismuth complexes and clusters, respectively. The measurements were conducted by the electrochemical process of the bismuth assembled dendritic poly-phenylazomethines.

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.

Metal clusters composed of several to several tens of atoms, in general, can be regarded as molecules rather than small nanoparticles. That is, a cluster bearing a different number of atoms is a “d...

Unusual complex formation of PtBr4 in THF was investigated for phenylazomethine dendrimer templates. The characteristics made it possible to reverse-order assemble platinum salts by changing the so...

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.

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 WCl

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.

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.

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.

Atomic-resolution electron microscopy elucidated single-molecule conformations of polynuclear coordination compounds., 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.

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.

Controlled reducing capsules with a specific number of reducing electrons were achieved by appropriately placed BH3 units in the dendritic poly-phenylazomethines (DPAs). Using the 1:1 coordination fashion on their basic branches with radius affinity gradient, the 4th generation DPA (DPAG4) possessing four BH3 units in the central positions was prepared as a template synthesizer for size-controlled ultra-small metal clusters. This was well-demonstrated by reduction of Ag, Pt and other metal ions resulting in monodispersed ultra-small clusters.

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.

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.

Metal assembly to a dendrimer can provide various functionalities based on the branched structure. Here, we researched assembly phenomena of bismuth salts in the phenylazomethine dendrimer and achieved enhancement of emission intensity per metal unit by using Bi(OTf)3. This enhancement suggested increasing of Bi–N coordination bonds derived from the bismuth units in the dendrimer.

Atomically-precise platinum subnanocluster (0.5–2 nm) catalysts were applied to the oxidation reaction of benzylalcohol with tert-butylhydroperoxide (TBHP) as the oxidant. The subnanoclusters (SNCs) exhibited higher catalytic activities than the commercially available platinum nanoparticle catalysts. A size-dependence of the catalytic activities exhibited a volcano-shaped behavior in these oxidation reactions.

On a subnanometer scale, an only one-atom difference in a metal cluster may cause significant transitions in the catalytic activity due to the electronic and geometric configurations. We now report the atomicity-specific catalytic activity of platinum clusters with significantly small atomicity, especially below 20. The atomic coordination structure is completely different from that of the larger face-centered cubic (fcc) nanocrystals. Here, an electrochemical study on such small clusters, in which the atomicity ranged between 12 and 20, revealed Pt19 as the most catalytically active species. In combination with a theoretical study, a common structure that leads to a high catalytic performance is proposed.

We report the synthesis of dodecanethiolate-protected platinum clusters by atomicity control using a dendrimer reactor followed by ligand-exchange extractions. Spectroscopic investigations suggested that a large cluster (Pt60) partially contains a metallic nature. In contrast, the small one (Pt12) exhibited a fully molecular-like nature with a significant structural rearrangement. figure Atomicity controlled platinum nano- and subnanoparticles in dendrimer reactors undergo surface ligand-exchange reactions. The large cluster (Pt60) partially contains a metallic nature whereas the small one (Pt12) exhibited fully molecular-like nature with a significant structural rearrangement.

Spherical dendrimers with phenylazomethine backbones are modifi ed onto atomically fl at mica or graphite substrates with a simple solvent based spin-coating method, and the resulting surfaces are observed by atomic force microscopy. Especially on the mica substrate, dendrimers form very fi ne and highly regular patterns with aligned nano-dot arrays and lines. An important observation is that the interval of each dot or line is ≈400 nm whereas previously reported self-assembling patterns exhibit longer intervals than 5 μm. It is revealed that spherical dendrimers with relatively low intermolecular interactions without any terminal modifi cations are suitable for the fi ne self-assembling pattern formation. This fact suggests that the regular pattern arises from a physical dissipative structure formation due to a fi ngering instability induced by Marangoni convection but not by anisotropic intermolecular interactions.

Superatoms, clusters that mimic the properties of elements different to those of which they are composed, have the potential to serve as building blocks for unprecedented materials with tunable properties. The development of a method for the solution-phase synthesis of superatoms would be an indispensable achievement for the future progress of this research field. Here we report the fabrication of aluminum clusters in solution using a dendrimer template, producing Al13 −, which is the most well-known superatom. The Al13 − cluster is identified using mass spectrometry and scanning transmission electron microscopy, and X-ray photoelectron spectroscopy is used to measure the binding energies. The superatomic stability of Al13 − is demonstrated by evaluating its tendency toward oxidation. In addition, the synthesis of Al13 − in solution enables electrochemical measurements, the results of which suggest oxidation of Al13 −. This solution-phase synthesis of Al13 − superatoms has a significant role for the experimental development of cluster science. Superatoms—clusters that exhibit some of the properties of elemental atoms—could serve as building blocks for functional materials, but their synthesis outside of the gas phase is highly challenging. Here, the authors use a dendrimer template to successfully produce Al13 − in solution.

Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5–13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt10) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis., The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster’s reactivity.

Multimetallic nanoclusters are synthesized using a dendrimer exhibited high activities for catalytic oxidation of hydrocarbons., The catalytic activity of alloy nanoparticles depends on the particle size and composition ratio of different metals. Alloy nanoparticles composed of Pd, Pt, and Au are widely used as catalysts for oxidation reactions. The catalytic activities of Pt and Au nanoparticles in oxidation reactions are known to increase as the particle size decreases and to increase on the metal-metal interface of alloy nanoparticles. Therefore, multimetallic nanoclusters (MNCs) around 1 nm in diameter have potential as catalysts for oxidation reactions. However, there have been few reports describing the preparation of uniform alloy nanoclusters. We report the synthesis of finely controlled MNCs (around 1 nm) using a macromolecular template with coordination sites arranged in a gradient of basicity. We reveal that Cu-Pt-Au MNCs supported on graphitized mesoporous carbon show catalytic activity that is 24 times greater than that of a commercially available Pt catalyst for aerobic oxidation of hydrocarbons. In addition, solvent-free aerobic oxidation of hydrocarbons to ketones at room temperature, using small amounts of a radical initiator, was achieved as a heterogeneous catalytic reaction for the first time.

Dendritic polyphenylazomethine (DPA) can form complexes with an unambiguous number of various metal ions, allowing the preparation of size-controlled sub-nanometer metal particles. Upon the deposition of the obtained metal nanoparticles on a substrate, the diameters usually tend to grow larger due to the aggregations. We now report that the deposition of such platinum (Pt) particles obtained by one of the DPA dendrimers (DPAG4) on a substrate without such aggregations. First, Pt nanoparticles supported in DPAG4 (DPAG4–Pt) were prepared from the complex between DPAG4 and 14PtCl4 (DPAG4–14PtCl4) in an organic solvent by a hydride reduction. The micelles of the dendrimer-surfactant composite containing monodispersed Pt nanoparticles in the shell are prepared in metal free buffer solutions. Because of the electro charge repulsion among the DPAG4 micelles, the monodispersed Pt particles prepared by DPAG4 can be deposited on the substrate without aggregation.

Classical metal-based nanomaterials come in two prominent types: a mononuclear or multinuclear complex chemically stabilized by organic ligands or a nanoparticle (also called a nanorod, nanosheet, or nanocrystal) physically stabilized by inorganic or polymer supports. Over the last decade, a class of superatoms that lies between these categories of materials has attracted attention because their properties are dramatically different from those typically ascribed to their component elements. Typically the superatoms include a specific, low number of metallic atoms. Because a one-atom difference can alter the properties of these superatoms, their synthesis must be ultraprecise, requiring one-atom resolution. To date, researchers have only been able to prepare monodisperse superatoms using gas-phase synthesis followed by purification through a flight tube. Though this technique provides monodisperse superatoms, it does not allow researchers to produce them in large quantites. Other researchers have proposed ligand-assisted liquid-phase synthesis as an alternative, but this technique is only useful for a few stable "magic number" clusters. Recently researchers have developed a new approach for the synthesis of superatoms that employs a novel class of molecular templates, which can define the number of metal ions or salts precisely. As a result, researchers can now synthesize nanoparticles or even subnanoparticles successfully. A dendrimer-type template has proven to be especially useful for ultraprecise control of the atomicity of the product, but it works with a full range of metal elements. In this Account, we highlight recent advances in the precise preparation of metal-assembling complexes using the dendrimer as a template. Next we discuss the selective assembly of subnanoparticles that utilize the dendrimer as a superatom synthesizer. The resulting subnanoparticles are almost monodisperse, and as a result, some of them exhibited distinctive characteristics based on their atomicity. For example, because of the quantum-size effect, the reduction in particle size of TiO2 and other metal-oxide subnanoparticles led to a significant shift in the band-gap energy. In addition, a miniaturized platinum particle less than 1 nm in diameter showed unexpectedly high catalytic activity for the oxygen reduction reaction (ORR) and other related reactions. Of particular note, in all these examples, this substantial change in their properties arose out of a single-atom difference in the atomicity. These results suggest that next-generation subnanoparticle design could play an important role in new materials and offer an additional palette of physical and chemical properties for new applications.

A relationship between the size of metal particles and their catalytic activity has been established over a nanometer scale (2-10 nm). However, application on a subnanometer scale (0.5-2 nm) is difficult, a possible reason being that the activity no longer relies on the size but rather the geometric structure as a cluster (or superatomic) compound. We now report that the catalytic activity for the oxygen reduction reaction (ORR) significantly increased when only one atom was removed from a magic number cluster composed of 13-platinum atoms (Pt13). The synthesis with an atomic-level precision was successfully achieved by using a dendrimer ligand as the macromolecular template strictly defining the number of metal atoms. It was quite surprising that the Pt12 cluster exhibited more than 2-fold catalytic activity compared with that of the Pt13 cluster. ESI-TOF-mass and EXAFS analyses provided information about the structures. These analyses suggested that the Pt12 has a deformed coordination, while the Pt13 has a well-known icosahedral atomic coordination as part of the stable cluster series. Theoretical analyses based on density functional theory (DFT) also supported this idea. The present results suggest potential activity of the metastable clusters although they have been "missing" species in conventional statistical synthesis.

Phenylazomethine dendrimers (DPA) can precisely incorporate metal chlorides onto the imine sites in a stepwise fashion. Such precise dendrimer–metal complexes allow the preparation of size-controlled subnanometer metal particles. We now propose a novel approach for the fabrication of size-controlled subnanometer metal oxide dots isolated on a substrate using two different-type dendrimers. One is a fourth-generation phenylazomethine dendrimer (DPAG4) and the other is a benzylether dendrimer (BzEG3) with a zinc porphyrin core. Even though the diameter of BzEG3 corresponds to that of DPAG4, BzEG3 has no metal-complexing site. Upon dip coating on a highly oriented pyrolytic graphite substrate by the mixed solution of the metal chloride-assembling DPAG4 molecules and BzEG3 molecules, the dendrimer monolayer was immobilized on the substrate. The concentration of the dendrimer mixture was determined in order to separate each DPAG4–metal chloride complex molecule by BzEG3. Monodispersed metaloxide nanodot arrays could be obtained from the dendrimer monolayer in which DPAG4–metal chloride complex molecule is well isolated by the BzEG3 as a spacer after the hydrolysis of metal chlorides followed by the complete removal of dendrimers. Copyright © 2013 John Wiley & Sons, Ltd.

A dendritic nanoshell based on rigid phenylazomethine units was synthesized up to fifth generation around a zinc porphyrin core. Due to the finely organized sparse architecture, accessibility to the core can be discriminated by the size of the molecules and ionic species. By using this function, the lifetime of the photochemically produced radical ion pair can be extended over 200 times longer along with a good quantum yield.