Carbon nanotube growth catalyzed by metal nanoparticles formed the seed effect of metal clusters.

Carbon nanotubes (CNTs) are useful nanomaterials owing to their distinct functions that depend on their structure and diameter; therefore, CNTs have recently attracted much attention. Catalytic chemical vapor deposition using metal nanoparticles as catalysts is one of the most useful methods for synthesizing CNTs. However, fine control of the CNT diameter has been technically difficult at the 1 nanometer level owing to the size distribution of metal nanoparticles and the difficulty in suppressing their aggregation during the CNT growth reaction.

Recent advances in atomic cluster synthesis: a perspective from chemical elements.

Despite its potential significance, "cluster chemistry" remains a somewhat marginalized topic within the chemistry field. However, atomic clusters with their unusual and unique structures and properties represent a novel material group situated between molecules and nanoparticles or solid matter, judging from both scientific standpoints and historical backgrounds. Surveying an entire material group, including all substances that can be regarded as a cluster, is essential for establishing cluster chemistry as a more prominent chemistry field.

Poly-phenylene jacketed tailor-made dendritic phenylazomethine ligand for nanoparticle synthesis.

Synthesizing metal clusters with a specific number of atoms on a preparative scale for studying advanced properties is still a challenge. The dendrimer templated method is powerful for synthesizing size or atomicity controlled nanoparticles. However, not all atomicity is accessible with conventional dendrimers.

Controlled Synthesis of Au 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 Au superatom have been investigated. However, previously reported methods were mainly depending on the thermodynamic stability of the aimed clusters.

Highly Accurate Synthesis of Quasi-sub-nanoparticles by Dendron-assembled Supramolecular Templates.

Quasi-sub-nanomaterials (1-3 nm) have been predicted to exhibit unique properties originating from the gray structures considered both bulk solids and molecules, while their synthesis is extremely difficult. The present study describes a new template synthesis method for quasi-sub-nanosized materials using a combination of coordination chemistry and polymer chemistry. Utilizing self-assembly of guest basic phenylazomethine dendron units onto host acidic core units with six tritylium cations, the dendron-assembled supramolecules were constructed easily and quantitatively without costly techniques.

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 -type atoms, while relatively rigid dendrimers composed only of -type atoms have rarely been reported.

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.

Quantum Materials Exploration by Sequential Screening Technique of Heteroatomicity.

Subnanoparticles (SNPs) exhibit unique properties and functions due to their extremely small particle sizes which extend into the quantum scale. Although the synthesis of SNPs requiring precise control of atomicity and composition has not been accomplished, we recently developed an atom-hybridization method (AHM) that realizes such atomic-level control using a macromolecular template. As a next step in the quest for innovative quantum materials, the practical creation of functional subnanomaterials will become a central subject.

Selective Hydroperoxygenation of Olefins Realized by a Coinage Multimetallic 1-Nanometer Catalyst.

The science of particles on a sub-nanometer (ca. 1 nm) scale has attracted worldwide attention. However, it has remained unexplored because of the technical difficulty in the precise synthesis of sub-nanoparticles (SNPs).

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.

Periodicity of molecular clusters based on symmetry-adapted orbital model.

The periodic table has always contributed to the discovery of a number of elements. Is there no such principle for larger-scale substances than atoms? Many stable substances such as clusters have been predicted based on the jellium model, which usually assumes that their structures are approximately spherical. The jellium model is effective to explain subglobular clusters such as icosahedral clusters.

Aerobic Toluene Oxidation Catalyzed by Subnano Metal Particles.

Subnanocatalysts (SNCs) containing various noble metals (Cu, Ru, Rh, Pd, or Pt) with sizes of approximately 1 nm were synthesized using dendritic poly(phenylazomethine)s as a macromolecular template. These materials exhibit high catalytic performance during toluene oxidation without the use of harmful solvents or explosive oxidants, resulting in the formation of valuable organic products, including benzoic acid as the major product. In particular, Pt SNC with a narrow particle size distribution exhibits extraordinary catalytic activity, with a turnover frequency of 3238 atom  h , which is 1700 times greater than that obtained by commercial Pt/C catalysts.

Atom-hybridization for synthesis of polymetallic clusters.

The chemistry of metal clusters on the sub-nanometer scale is not yet well understood because metal clusters, especially multimetallic clusters, are difficult to synthesize with control over size and composition. The template synthesis of multimetallic sub-nanoclusters is achieved using a phenylazomethine dendrimer as a macromolecular template. Its intramolecular potential gradient allows the precise uptake of metal precursor complexes containing up to eight elements on the template.

Nanomaterials design for super-degenerate electronic state beyond the limit of geometrical symmetry.

Spherical atoms have the highest geometrical symmetry. Due to this symmetry, atomic orbitals are highly degenerate, leading to closed-shell stability and magnetism. No substances with greater degrees of degeneracy are known, due to geometrical limitations.

Mechano-, thermo-, solvato-, and vapochromism in bis(acetato-κO)[4'-(4-(diphenylamino)phenyl)](2,2':6',2''-terpyridine-κN,N',N'')zinc(ii) and its polymer.

The titled complex exhibits multi-functional luminochromism in the solid state, despite its simple chemical structure. The complex shows solid-state vapochromism and mechanochromism. The polymer analogue of the complex undergoes solvatochromism and thermochromism.

Coordination Nanosheets Based on Terpyridine-Zinc(II) Complexes: As Photoactive Host Materials.

Photoluminescent coordination nanosheets (CONASHs) comprising three-way terpyridine (tpy) ligands and zinc(II) ions are created by allowing the two constitutive components to react with each other at a liquid/liquid interface. Taking advantage of bottom-up CONASHs, or flexibility in organic ligand design and coordination modes, we demonstrate the diversity of the tpy-zinc(II) CONASH in structures and photofunctions. A combination of 1,3,5-tris[4-(4'-2,2':6',2″-terpyridyl)phenyl]benzene (1) and Zn(BF) affords a cationic CONASH featuring the bis(tpy)Zn complex motif (1-Zn), while substitution of the zinc source with ZnSO realizes a charge-neutral CONASH with the [Zn(μ-OSO)(tpy)] motif [1-Zn(SO)].

A simple zinc(ii) complex that features multi-functional luminochromism induced by reversible ligand dissociation.

The authors create a zinc(ii) complex featuring a simple chemical structure but multi-functional luminochromism. Reversible dissociation/association between the zinc center and the terpyridine ligand plays a key role in the multi-functional luminochromism.

Photophysical Properties and Adsorption Behaviors of Novel Tri-Cationic Boron(III) Subporphyrin on Anionic Clay Surface.

Two types of +3-charged subporphyrin derivatives with m- and p-methylpyridinium as the meso-aryl substituents were designed and synthesized. Their photophysical properties with and without anionic saponite clay were investigated. These cationic subporphyrins were suitably designed for adsorption on the saponite nanosheet surface with their photoactivity.

Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand.

Heteroleptic zinc(II) complexes synthesized using achiral dipyrrinato and chiral bis(oxazoline) ligands show bright fluorescence with quantum efficiencies of up to 0.70. The fluorescence originates from the (1)π-π* photoexcited state localized exclusively on the dipyrrinato ligand.

Pinning effect for photoisomerization of a dicationic azobenzene derivative by anionic sites of the clay surface.

The photoisomerization behaviour of a dicationic azobenzene derivative on the inorganic surface was examined. The isomerization reaction was controlled by the charged array of the inorganic surface due to the "pinning effect" because of the electrostatic interaction between anionic charged sites on the inorganic surface and cationic charged sites in dye molecules.

Photochemical properties of mono-, tri-, and penta-cationic antimony(V) metalloporphyrin derivatives on a clay layer surface.

Three types of mono-, tri-, and penta-cationic antimony(V) porphyrin derivatives (Sb(V)Pors) were synthesized, and their photochemical properties on the anionic clay were systematically investigated. Sb(V)Por derivatives are dihydroxo(5,10,15,20-tetraphenylporphyrinato)antimony(V) chloride ([Sb(V)(TPP)(OH)2](+)Cl(-)), dihydroxo[5,10-diphenyl-15,20-di(N-methyl-pyridinium-4-yl)porphyrinato]antimony(V) trichloride ([Sb(V)(DMPyP)(OH)2](3+)3Cl(-)), and dihydroxo[5,10,15,20-tetrakis(N-methyl-pyridinium-4-yl)porphyrinato]antimony(V) pentachloride ([Sb(V)(TMPyP)(OH)2](5+)5Cl(-)). The photochemical behaviors of three cationic Sb(V)Pors with and without clay were examined in aqueous solution.