D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Computational Analysis Reveals a Critical Point Mutation in the N-Terminal Region of the Signaling Lymphocytic Activation Molecule Responsible for the Cross-Species Infection with Canine Distemper Virus

Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility.     

Photoinduced Betaine Generation for Efficient Photothermal Energy Conversion

The conversion of solar energy to thermal, chemical, or electrical energy attracts great attention in chemistry and physics. There has been a considerable effort for the efficient extraction of photons throughout the entire solar spectrum. In this work light energy was efficiently harvested by using a long-lived betaine photogenerated from an acridinium-based electron donor–acceptor dyad. The photothermal energy-conversion efficiency of the dyad is significantly enhanced by simultaneous illumination with blue (420–440 nm) and yellow (>480 nm) light in comparison with the sum of the conversion efficiencies for individual illumination with blue or yellow light. The enhanced photothermal effect is due to the photogenerated betaine, which absorbs longer-wavelength light than the dyad, and thus the dyad–betaine combination is promising for efficient photothermal energy conversion. The mechanisms of betaine generation and energy conversion are discussed on the basis of steady-state and transient spectral measurements.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.     

Formation of an Azaruthenacyclopentadiene Skeleton via Ammonia Activation by an Electron-Deficient Ru3 Cluster

A dicationic triruthenium complex containing a μ₃-η³-C₃ ring, [(Cp*Ru)₃(μ₃-η³-C₃MeH₂−)(μ₃-CH)(μ-H)]²⁺ ( 1 a , Cp*=η⁵-C₅Me₅), reacted with ammonia to yield a μ-amido complex, [(Cp*Ru)₃(μ₃-η³-CHCMeCH) (μ₃-CH)(μ-NH₂)]²⁺ ( 5 ), via N−H bond scission. Subsequent treatment with base resulted in C−N bond formation to yield a μ₃-η²:η²-1-azabutadien-4-yl complex, [(Cp*Ru)₃(μ₃-CH)(μ₃-η²:η²-NH=CH−CMe=CH−)]⁺ ( 6 a ). The azaruthenacyclopentadiene skeleton was alternatively synthesized by the photolysis of mono-cationic complex [(Cp*Ru)₃(μ₃-η³-C₃RH₂−)(μ₃-CH)]⁺ ( 2 a ; R=Me, 2 b ; R=H) in the presence of ammonia. The C₃ ring skeleton was broken via the electron transfer to the π*(C−C) orbital in the C₃ ring, and a transiently generated unsaturated μ₃-allylic species can take up ammonia, resulting in N−H bond scission followed by C−N bond formation.     

Two‐Step direct arylation for synthesis of naphthalenediimide‐based conjugated polymer

A naphthalenediimide (NDI)‐based conjugated polymer was synthesized by a two‐step direct C‐H arylation sequence. In the first step, two ethylenedioxythiophene units were coupled to NDI by direct arylation. In the second step, the direct arylation polycondensation of the monomer, formed in the first step, with 2,7‐dibromo‐9,9‐dioctylfluorene afforded the corresponding NDI‐based conjugated polymer ( PEDOTNDIF ) with molecular weight of 21,500 in 91% yield. The optical and electrochemical properties of the polymer were evaluated. The polymer showed ambipolar behavior in organic field‐effect transistors (OFETs). The electron mobility of PEDOTNDIF was estimated to be 2.3 × 10^?6 cm² V^?1 s^?1 using an OFET device with source‐drain (S‐D) Au electrodes. A modified OFET device with S‐D MgAg electrodes increased the electron mobility for PEDOTNDIF to 1.0 × 10^?5 cm² V^?1 s^?1 due to the more suitable work function of these electrodes, which reduced the injection barrier to the semiconducting polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1401–1407     

One-Step Synthesis of Cyclobutene-Annulated Fullerenes through a Cascade Reaction

The physicochemical properties of fullerene-based materials typically vary depending on the type and mode of addition of functional groups; therefore, developing fullerene derivatives with novel structures is imperative for further progress in materials science. In this study, we develop an efficient one-step strategy for synthesizing cyclobutene-annulated fullerene derivatives (cyclobutenofullerenes) and characterize their electronic properties. Despite the steric strain, cyclobutenofullerenes can be easily prepared via a one-step reaction of C₆₀ with a secondary propargylic phosphate. Structural analysis of the reaction intermediates suggests that the cascade reaction proceeds through a formal [2+2] cycloaddition of C₆₀ with an allene, caused by the 1,3-migration of the propargylic phosphate, followed by an additional 1,3-migration and the subsequent 1,2-elimination of the phosphodiester moiety.     

Synthesis and Pyrolysis of Fullerenol-stabilized Pt Nanocolloids as a unique Approach to Pt-doped Carbon

An aqueous colloidal dispersion of Pt nanoparticles (NPs) stabilized by fullerenol C₆₀(OH)₁₂ (Pt:C₆₀(OH)₁₂) was successfully synthesized via liquid-phase chemical reduction. The subsequent pyrolysis of Pt:C₆₀(OH)₁₂ at different temperatures was conducted to afford Pt-doped carbon with different chemical compositions (Pt:C60ⁿ). X-ray absorption spectroscopy (XAS) and Infrared (IR) absorption spectroscopy and thermogravimetric measurements revealed that the thus-prepared nanocomposite consists of Pt NPs and high valent Pt-C₆₀(OH)₁₂ complex. One distinct feature of C₆₀(OH)₁₂ matrix as catalyst support is the suppression of size growth of Pt NPs during the pyrolysis up to 300 °C. Electrochemical experiments using cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were performed to find that Pt:C60³⁰⁰ (pyrolyzed at 300 °C) exhibited higher activity than others, that was attributed to the π-extended feature of the as-obtained carbon.     

Limit theorems for the pre-averaged Hayashi–Yoshida estimator with random sampling

We will focus on estimating the integrated covariance of two diffusion processes observed in a nonsynchronous manner. The observation data is contaminated by some noise, which possibly depends on the time and the latent diffusion processes, while the sampling times also possibly depend on the observed processes. In a high-frequency setting, we consider a modified version of the pre-averaged Hayashi–Yoshida estimator, and we show that such a kind of estimator has the consistency and the asymptotic mixed normality, and attains the optimal rate of convergence.