Photothermal Oxidation of Cinnamyl Alcohol with Hydrogen Peroxide Catalyzed by Gold Nanoparticle/Antimony-Doped Tin Oxide Nanocrystals

Gold nanoparticles with different mean sizes were formed on antimony-doped tin oxide nanocrystals by the temperature-varied deposition-precipitation method (Au/ATO NCs). Au/ATO NCs possess strong absorption in the near-infrared region due to Drude excitation in addition to the localized surface plasmon resonance (LSPR) of AuNPs around 530 nm. Au/ATO NCs show thermally activated catalytic activity for the oxidation of cinnamyl alcohol to cinnamaldehyde by hydrogen peroxide. The catalytic activity increases with a decrease in the mean Au particle size (d_Au) at 5.3 nm≤d_Au≤8.2 nm. Light irradiation (λ_ex >660 nm, ∼0.5 sun) of Au/ATO NCs increases the rate of reaction by more than twice with ∼95 % selectivity. Kinetic analyses indicated that the striking enhancement of the reaction stems from the rise in the temperature near the catalyst surface of ∼30 K due to the photothermal effect of the ATO NCs.     

N-Doping of Polyaromatic Capsules: Small Cavity Modification Leads to Large Change in Host–Guest Interactions

To gain insight into the host functions of a nanocavity encircled by both polyaromatic panels and heteroatoms, nitrogen-doped polyaromatic capsules were successfully synthesized from metal ions and pyridine-embedded, bent anthracene-based ligands. The new capsules display unique host–guest interactions in the isolated cavities, which are distinct from those of the undoped analogues. Besides the inclusion of Ag⁺ ions, the large absorption change of fullerene C₆₀ and altered emission of a BODIPY dimer are observed upon encapsulation by the present hosts. Moreover, the N-doped capsule exhibits specific binding ability toward progesterone and methyltestosterone, known as a natural female and synthetic male hormone, respectively, in water.     

Dimesitylborylethynylated Arenes: Unique Electronic and Photophysical Properties Caused by Ethynediyl (C≡C) Spacers

Herein, we report the synthesis and electrochemical and photophysical properties of aromatic hydrocarbons having one or two dimesitylborylethynyl peripherals. The mono- ( 1 ) and diboryl compounds ( 2 ), readily prepared by nucleophilic substitution reaction, are fairly stable to air and moisture in the solid state. The inserted ethynediyl (C≡C) spacer cancels the steric hindrance between the bulky dimesitylboryl groups and aromatic rings, leading to effective π conjugation over the B−C≡C−Ar linkages, as revealed by cyclic voltammetry. Despite the small structural differences, the photophysical properties of the benzene, naphthalene, and anthracene derivatives are different. Virtually no emission was observed from the benzene derivatives, whereas the anthracene derivatives emitted with high quantum yields both in solution and in the solid state. Notably, the naphthalene derivatives showed aggregation-induced emission behavior. Unlike the common sterically congested triarylborane derivatives reported so far, the anthracene derivatives showed π–π*-type absorption and emission bands, which derive from efficient intramolecular orbital interactions between the boron centers and anthracene moieties, as supported by DFT calculations. As a result, the dimesitylborylethynyl substituents effectively lower the LUMO levels of the aromatic hydrocarbon parts, whereas the HOMO levels are almost unaffected, thereby leading to materials with controllable HOMO–LUMO gaps.     

Organometallic Molecular Wires with Thioacetylene Backbones,trans-{RS-(C≡C)n}2Ru(phosphine)4: High Conductance through Non-Aromatic Bridging Linkers

In this work, the design, synthesis, and single-molecule conductance of ethynyl- and butadiynyl-ruthenium molecular wires with thioether anchor groups [RS=n-C₆H₁₃S, p-tert-Bu−C₆H₄S), trans-{RS−(C≡C)_n}₂Ru(dppe)₂ (n=1 ( 1^R ), 2 ( 2^R ); dppe: 1,2-bis(diphenylphosphino)ethane) and trans-(n-C₆H₁₃S−C≡C)₂Ru{P(OMe)₃}₄ 3^hex ] are reported. Scanning tunneling microscope break-junction study has revealed conductance of the organometallic molecular wires with the thioacetylene backbones higher than that of the related organometallic wires having arylethynylruthenium linkages with the sulfur anchor groups, trans-{p-MeS−C₆H₄-(C≡C)_n}₂Ru(phosphine)₄ 4 ⁿ (n=1, 2) and trans-(Th−C≡C)₂Ru(phosphine)₄ 5 (Th=3-thienyl). It should be noted that the molecular junctions constructed from the butadiynyl wire 2^R , trans-{ Au −RS−(C≡C)₂}₂Ru(dppe)₂ ( Au : gold metal electrode), show conductance comparable to that of the covalently linked polyynyl wire with the similar molecular length, trans-{ Au −(C≡C)₃}₂Ru(dppe)₂ 6³ . The DFT non-equilibrium Green's function (NEGF) study supports the highly conducting nature of the thioacetylene molecular wires through HOMO orbitals.     

Polycationic‐Shelled Capsular and Tubular Nanostructures and Their Anionic–Guest Binding Properties

For the development of novel nanospace with unique electrostatic character, we prepared new capsular and tubular nanostructures by the quantitative assembly of metal ions and bent bisacridinium ligands. The capsule and tube have closed spherical and open cylindrical cavities, respectively, with diameters of around 1 nm surrounded by cationic polyaromatic panels. Thanks to the facile synthetic protocol (three steps), another polycationic capsule with an elliptical nanocavity was also prepared by using an elongated ligand. In spite of the absence of pendant hydrophilic groups, the spherical polyaromatic capsule shows sufficient water solubility due to the polycationic shell. Moreover, the highly cationic cavity (12+) can selectively encapsulate anionic organic compounds in water.     

Solubility Switching of Metallophthalocyanines and Their Larger Derivatives upon Encapsulation

Metallophthalocyanines (MPcs) are very useful pigments but scarcely soluble without appropriate functional groups in common solvents. Herein, we report that bent polyaromatic amphiphiles act as excellent solubilizing reagents for nonfunctionalized MPcs and larger MPc derivatives (e.g., CuPc, perhalogenated CuPcs, Cu‐naphthalocyanine, CuPc polymers, and double‐decker MPcs) in neutral water upon encapsulation. The resultant MPc nanocomposites display high stability towards heat and pH change. More importantly, the encapsulated MPcs can be released by simple protocols under mild conditions both into a bulk solvent and onto glass or polymer plates.     

Selective Host–Guest Interactions of a Transformable Coordination Capsule/Tube with Fullerenes

An M₂L₄ coordination capsule or an M₂L₂ coordination tube was selectively formed by the combination of Hg^II hinges and bent bispyridine ligands. The two structures reversibly interconvert at room temperature in response to modulation of the metal‐to‐ligand ratio and exhibit different host–guest interaction behavior. The capsule alone encapsulates large spherical molecules, fullerenes C₆₀ and C₇₀, and the bound guests are released upon capsule‐to‐tube transformation by the simple addition of metal ions.     

Synthesis of Au–Pd bimetallic nanoparticles under energetic irradiation fields

Bimetallic Au–Pd nanoparticles were synthesized under high-energy irradiation fields (1.17 and 1.33 MeV γ-rays, 9 MeV electrons, and 1.6 GeV C ions) from solutions containing Au³⁺ and Pd²⁺ and cationic surfactant (sodium dodecyl sulfate). Particles synthesized by the irradiation were observed using conventional transmission electron microscope (TEM) and annular dark-field scanning transmission electron microscopy (ADF-STEM). The particles synthesized by γ-rays and C ion irradiation exhibit core–shell structure with a Au-core and a Pd-shell. The dependence of the size distribution of nanoparticles on the dose rate is discussed.