Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 91 , Issue 5
Showing 1-17 articles out of 17 articles from the selected issue
 
  • Takuma Kawai, Satoshi Nakao, Hiroyuki Nishide, Kenichi Oyaizu
    2018 Volume 91 Issue 5 Pages 721-727
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Redox-active polymers with large charge-storage density are candidates for electrode-active materials in next-generation energy storage devices, due to their swift charge-discharge capabilities and their inherent characteristics of redox reactions that occur without significant structural changes, leading to their highly energy-efficient and durable performance. Here we report poly(diphenanthrenequinone-substituted norbornene) (PQN) as a novel class of organic electrode-active material. A Li coin cell composed of the PQN/carbon composite electrode as the cathode exhibited 2.8 V (V vs. Li/Li+) and great cycle performance maintaining a capacity higher than 100 mAh/g for more than 100 cycles at 60 C (i.e. in 1 min charging and discharging). Among many types of o-quinone-containing polymers for Li-ion batteries reported so far, the present research provides the first example of introducing phenanthrenequinone as the pendant group per repeating unit of polymers, which proved to be especially advantageous in terms of robustness and cyclability by virtue of the fused-ring structure to protect the reactive positions of the o-benzoquinone. We also report that the functional group tolerance against many types of redox-active groups, which we have established for the initiator and the propagating end of norbornene derivatives, apply for the phenanthrenequinone-substituted monomer, giving rise to a reversible redox activity.

  • Akkapol Suea-Ngam, Monpichar Srisa-Art, Yuji Furutani
    2018 Volume 91 Issue 5 Pages 728-734
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Polydimethylsiloxane (PDMS) is a well-known material used in making microfluidic devices through soft lithography. PDMS strongly absorbs infrared (IR) light in the mid infrared region, which can be alleviated by using thin-film PDMS devices. However, IR detection with PDMS devices usually requires an IR-transparent backbone material. Here, we report a microfluidic system using a 160 µm PDMS thin-film device (50-µm path length) without a supporting backbone for IR spectroelectrochemistry (IR-SEC). The PDMS device is assembled with four layers: microchannel-supporting window, microchannel thin film, electrode-embedded thin film, and electrode-supporting window. In this work, mapping of ferrocyanide oxidation was investigated under an IR microscope. An electrochemical reaction, occurring between the working and counter electrodes, was observed clearly. Moreover, the electron-transfer process of ferrocyanide oxidation was investigated from the IR absorbance spectrum. This mapping study demonstrates that the relationship between the electrochemical reactants and products partly agree well with the Nernst equation. Accordingly, PDMS thin-film devices have the capability for studying electrochemical reactions by using IR-SEC measurements with low sample consumption.

  • Toshiki Yamaji, Takeshi Saito
    2018 Volume 91 Issue 5 Pages 735-740
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    The analysis of a second-order pattern on a proton NMR spectrum is proposed using a multi field NMR measurement, a spectral simulation, a DFT calculation and a solvent effect study. The ordinary 9.4 T proton NMR measurement of 1,3-dichloro-2-nitrobenzene in organic solvents gave the AB2 spectrum showing the second-order pattern. The higher field, 14.1 T proton NMR measurement gave the spectrum close to the AX2 showing the first-order pattern with a little roofing. Then the peak assignments were confirmed by the spectral simulation using the NMR parameters obtained from each experimental spectra. Finally, the NMR parameters are discussed from the results of the DFT calculation and the solvent effect study.

  • Hiroki Yamashita, Takaaki Ogami, Kiyoshi Kanamura
    2018 Volume 91 Issue 5 Pages 741-746
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Hollow Al2O3 microfibers were successfully synthesized via a novel hydrothermal method using cotton fiber as a template followed by annealing. The hollow Al2O3 microfibers annealed at 1200 °C for 5 h contained no impurity phases, and the Al2O3 composing the microfibers was confirmed to exhibit the trigonal unit cell of α-Al2O3 with R-3c space-group symmetry. The synthesized hollow Al2O3 microfibers were 5–15 µm in diameter, with walls 500–800 nm thick; the walls were composed of Al2O3 primary particles 100–200 nm in diameter. The specific heat capacity of the synthesized hollow Al2O3 microfibers was approximately the same as that reported in the literature for α-Al2O3. In addition, the annealing temperature of the hollow Al2O3 microfibers was studied to elucidate their mechanism of formation. The chemical and physical properties of the synthesized hollow Al2O3 microfibers indicate that they can be used as a thermal insulation material.

  • Masashi Yoshikawa, Hiroya Shiba, Hiroaki Wada, Atsushi Shimojima, Kazu ...
    2018 Volume 91 Issue 5 Pages 747-753
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Two types of cyclododecasiloxanes possessing Si–H and Si–OEt side groups were polymerized by the Piers-Rubinsztajn (P-R) reaction. Cyclododecasiloxane possessing both methyl and ethoxydimethylsilyl side groups (Cyclo12-Me-SiMe2(OEt)) was synthesized by ethoxylation of cyclododecasiloxane possessing both methyl and dimethylsilyl side groups (Cyclo12-Me-SiHMe2). Cyclo12-Me-SiMe2(OEt) and Cyclo12-Me-SiHMe2 were polymerized by the P-R reaction, using B(C6F5)3 as a catalyst. The original cyclic structures were retained after the reaction without cleavage of the Si–O–Si bonds. Dimethylsilane elimination between two side –SiHMe2 groups and the consecutive siloxane-bond formation occurred concomitantly during the main P-R reaction. The effectiveness of the P-R reaction between oligosiloxanes toward preparation of polyorganosiloxanes with well-defined architectures has been demonstrated.

BCSJ Award Article
  • Peerathat Pinpithak, Ashish Kulkarni, Hsin-Wei Chen, Masashi Ikegami, ...
    2018 Volume 91 Issue 5 Pages 754-760
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Herein, for the first time, a concept of co-sensitization of the D149 dye with methylammonium lead bromide (MAPbBr3) perovskite is presented in solid-state dye-sensitized solar cells (ss-DSSCs). A thin film was fabricated by employing ~500 nm TiO2 mesoporous layer sensitized with metal-free organic dye D149 and MAPbBr3 as a co-sensitizer which absorb long wavelength (green) and short wavelength (blue) light, respectively. With panchromatic spectral sensitivity up to ~680 nm, the co-sensitized device yielded power conversion efficiency up to 3.1% by means of tuning the loading amounts of perovskite with respect to dye. We found that small amounts of MAPbBr3 can mitigate dye aggregation and can improve the light harvesting property of the device sensitized with a D149 dye. Additionally, electrochemical impedance spectroscopic (EIS) analysis of dye/perovskite co-sensitized device showed efficient charge transfer between dye (embedded with perovskite crystal) and TiO2. This study opens up the possibilities of use of lead bromide perovskite as co-sensitizer in ss-DSSCs.

    Herein, for the first time, we attempt to improve light harvesting properties of indoline sensitizer (D149) based solid-state dye-sensitized solar cell by co-sensitization with green light absorbing methylammonium lead bromide perovskite (MAPbBr3). We found that a small amount of MAPbBr3 (0.16 M) can effectively reduce dye aggregation and simultaneously improve light harvesting property compared with the individual dye with the best efficiency up to 3.1%. Fullsize Image
     
Award Account
Lectureship Award in Asian International Symposium for 2017
  • Rajesh Kumar Ulaganathan, Yi-Hsuan Chang, Di-Yan Wang, Shao-Sian Li
    2018 Volume 91 Issue 5 Pages 761-771
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Atomically thin two-dimensional (2D) materials have been a famous and fascinating material in recent years due to the potential to replace conventional semiconducting bulk electronic materials. To control the performance of 2D materials, many methods have been proposed, including physical and chemical ways, to manipulate the electronic, atomic and microscopic properties. In this work, we would like to present a physical method based on the interactions of 2D materials with light to influence the 2D material properties and device performance. By reviewing some recent published work, we will show how effective the light can be to functionalize 2D materials. The fundamental fluorescence phenomenon and current applications using 2D materials in optoelectronics, such as photodetectors, solar cells and light emitting diodes, to obtain improved device properties will also be discussed.

    Atomically thin 2D materials have already shown great potential in electronics due to the excellent electrical properties. The outstanding performance in electronics underrated the potential of 2D materials to be influenced by light. In this review, we shed light on the interactions of 2D materials with photons, through fluorescence, light-induced photo-doing effect, and the applications utilized in optoelectronics. Fullsize Image
     
 
  • Tomonari Tanaka, Masaru Okamoto
    2018 Volume 91 Issue 5 Pages 772-777
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Lectin and temperature dual-responsive glycosylated block copolymers, composed of a hydrophilic polymer backbone comprising poly(N-isopropylacrylamide) (PNIPAm) and polyacrylamide (PAAm), were synthesized by consecutive RAFT polymerization reactions. PNIPAm was synthesized by RAFT polymerization using a trithiocarbonate derivative for use as a macro chain transfer agent (CTA) in post-RAFT polymerization with a lactose-carrying acrylamide derivative used as a monomer substrate to obtain block copolymers. The resulting glycosylated block copolymers were responsive to temperature at around 33 °C (lower critical solution temperature; LCST) and formed aggregates 200 nm in diameter above the LCST in aqueous media. The aggregates specifically interacted with lectin in aqueous media above the LCST, forming precipitated conjugates. When the temperature was decreased below the LCST, the conjugate dissociated and dissolved into the aqueous medium. The conjugates composed of block copolymer and lectin are reversible and respond to changes in temperature.

  • Tomiko M. Suzuki, Takamasa Nonaka, Kosuke Kitazumi, Naoko Takahashi, S ...
    2018 Volume 91 Issue 5 Pages 778-786
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    A highly crystalline, 10 nm-sized red rust water oxidation catalyst composed of pure β-phase FeOOH(Cl) nanorods (ca. 3 × 13 nm) doped with Ni ions (β-FeOOH(Cl):Ni) and surface-modified with amorphous Ni(OH)2 (a-Ni(OH)2, at a Ni to Fe ratio of 22 at.%) was synthesized by a facile one-pot process at room temperature. The overpotential during the electrochemical oxygen evolution reaction (OER) over the β-FeOOH:Ni/a-Ni(OH)2 stacked nanorod anodes was 170 mV, and an OER current of 10 mA/cm2 was obtained at an overpotential of 430 mV in a 0.1 M KOH solution. X-ray absorption fine structure analysis, Mössbauer spectroscopy, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, X-ray diffraction and impedance spectroscopy suggested that surface modification with the a-Ni(OH)2 lowered the OER overpotential of β-FeOOH(Cl):Ni, resulting in the very high current density at low potential compared with Fe-rich oxide and oxyhydroxide electrodes reported previously. Mössbauer spectroscopy suggested interaction between Fe and Ni species, which may be crucial evidence for the enhanced activity in the Fe-rich OER system.

  • Yuji Miyazato, Kouta Imaizumi, Rikako Tanaka, Tohru Wada, Nobuyuki Mat ...
    2018 Volume 91 Issue 5 Pages 787-789
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    The [{Fe(Me3tacn)}2(µ-P2O7)(µ-HPO4)]·12H2O dinuclear Fe2(III, III) complex was prepared. The HPO42− bridge in the complex arises from hydrolysis of the pyrophosphate bound to the Fe(III) centers in the trinuclear [{Fe(Me3tacn)}3(P2O7)2]+ intermediate. Electrochemical reduction of this complex at pH <3.2 results in dissociation of the H2PO4 bridge.

90th Commemorative Account: Fascinating Molecules and Reactions
Award Account
The Chemical Society of Japan Award for Creative Work for 2016
  • Nobuto Yoshinari, Takumi Konno
    2018 Volume 91 Issue 5 Pages 790-812
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    In this account, we focus on the stereochemical and chiral behavior of S-bridged multinuclear and metallosupramolecular coordination compounds that are derived from mononuclear metal complexes with cysteine (H2cys) or penicillamine (H2pen). The mononuclear complexes act as versatile metalloligands with amine and/or carboxyl groups, in addition to the thiol groups, as donor sites, allowing them to form a large variety of coordination compounds in combination with additional metal ions. Several chiral elements, such as chiral metal centers, asymmetric bridging sulfur atoms, and molecular and supramolecular helicity, in addition to asymmetric carbon atoms, are created in the resulting molecular and crystal structures, and their absolute configurations are often controlled to produce a single kind of homochiral species. In addition, this metalloligand approach leads to several unique chiral phenomena, such as stimulus-responsive chiral switching/inversion based on geometrical changes in metal centers, highly efficient chiral recognition between multinuclear complex cations and anions, and unusual spontaneous resolution behavior, in the resulting coordination systems.

    Since the establishment of coordination chemistry by A. Werner, the creation of chiral metal complexes has been one of the most important topics in the field of coordination chemistry. In this account, we focus on the stereochemical and chiral behavior of S-bridged multinuclear and metallosupramolecular compounds that are derived from metalloligands with cysteine or penicillamine. Fullsize Image
     
 
  • Manami Iizuka, Yuto Nakagawa, Yuma Moriya, Eiichi Satou, Atsuhiro Fuji ...
    2018 Volume 91 Issue 5 Pages 813-823
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    In this study, we compare and investigate both microscopic molecular packing and mesoscopic morphogenetic behavior in two-dimensional (2D) organized films/three-dimensional (3D) solids of three kinds of Gemini-type diamide surfactants that systematically differ in terms of their chemical structure. The gelation of the surrounding medium is promoted by growing crystalline nanofibers of these surfactants, and the disappearance of these nanofibers and solvent reflow are caused by the application of a force on the corresponding gel because these surfactant molecules are considered potential thixotropic agents. The layer structure and sub-cell in the 3D crystals of surfactants are formed by the association of van der Waals force and hydrogen bonding because the mechanism responsible for crystalline nanofiber formation is intermolecular hydrogen bonding. In the monolayer on the water surface, only surfactant molecules having a hydroxyl group in the hydrophobic chain formed crystalline nanofibers. The introduction of hydroxyl groups into the hydrophobic chains also promoted a single-phase molecular conformation in 3D crystals. However, the absence of hydroxyl groups in the hydrophobic chain promoted the growth of the nanofibers in the cast film, whereas the introduction of hydroxyl groups in the hydrocarbons improves the thixotropic property itself. In addition, the epitaxial growth of nanofibers upon the addition of a growth aid was promoted by the absence of hydroxyl groups.

  • Shiladitya Chatterjee, Matthew R. Linford
    2018 Volume 91 Issue 5 Pages 824-828
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Pattern Recognition Entropy (PRE) is a summary statistic for comparing and understanding spectra. Here we introduce the concept of the ‘reordered spectrum’ in the context of PRE as an intuitive, visual representation of spectra. The shapes of reordered (sorted) spectra correlate with their PRE values and help explain them. We illustrate these concepts with liquid chromatography-mass spectrometry (LC-MS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS) spectra. Reordered spectra should have value beyond PRE for comparing and understanding spectra.

90th Commemorative Account: Fascinating Molecules and Reactions
Award Account
The Chemical Society of Japan Award for Young Chemists for 2016
  • Satoru Hiroto
    2018 Volume 91 Issue 5 Pages 829-838
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Creation of novel π-conjugated molecules is an important topic. In this account, one idea for creation of π-conjugated molecules by using distorted conformation has been demonstrated. Planarization of distorted molecules enabled synthesis of heteroatom-containing porphyrin derivatives. Furthermore, dearomatization reaction proved effective to construct distorted conformations from planar π-conjugated molecules under mild reaction conditions. According to this protocol, we have succeeded in the synthesis of heteroatom-containing curved π-conjugated molecules, which have never been achieved by conventional protocols. In particular, a nitrogen embedded buckybowl is the first example of a buckybowl with a heteroatom in its central position, exhibiting unique properties due to incorporation of heteroatom with a curved π-surface.

    I succeeded in the synthesis of novel π-conjugated molecules based on the strategies of “distortion-to-planar” and “planar-to-distortion”. The first strategy produced a cyclic tetraindole, and 10-heterocorroles as novel porphyrinoids. The second strategy enabled construction of heteroatom-containing curved π-conjugated molecules under the laboratory conditions. Fullsize Image
     
 
90th Commemorative Account: Self-Organization
  • Xianhe Liu, Jean G. Riess, Marie Pierre Krafft
    2018 Volume 91 Issue 5 Pages 846-857
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    After a brief reminder of the specific properties of fluorocarbons, fluorinated chains and molecular fluorocarbon-hydrocarbon diblocks (semifluorinated alkanes, CnF2n+1CmH2m+1, FnHm) that account for their exceptional aptitude for self-organization, we review recent advances on the self-assembled surface nanodomains that FnHm diblocks form on water and solid surfaces, their shape and size characteristics, and their hierarchical organization into structures of higher complexity. Remarkably indeed, FnHm diblocks, when spread as Langmuir monolayers on water, self-assemble into circular mesoscopic nanodomains that exist even in the absence of lateral pressure, and self-organize into regular hexagonal arrays upon compression. These surface domains can be transferred essentially unchanged onto solid surfaces. They can also be obtained by direct casting or spin coating of solutions of diblocks on solids, or by spontaneous formation on liquid crystals. The nanodomains retain their size, shape and organization upon compression and, amazingly, even beyond the collapse of their Langmuir monolayers. The domain-patterned films display uncommon rheology, with predominantly elastic monolayers, and two-dimensional gels were generated, including at zero surface pressure. The formation and behavior of surface domains from related tri- and tetrablocks have also been reported. A tetrablock afforded the first example of pressure-driven stacking of self-assembled nano-objects. The domain-patterned films constitute attractive templates for organizing nanoparticles in components of electronic devices and sensors, and for fabricating ordered mesoporous solids. Most recently, a novel aggregation mode was found for FnHm diblocks, namely their crystallization into micron-size polycrystalline two-dimensional radial and/or ring-banded spherulites. Applications in medicine and materials science are being investigated.

    Numerous studies involving various semifluorinated alkanes, spreading techniques and experimental conditions have determined that formation and ordering of molecular surface nanodomains on water and solid supports (including liquid crystals) are intrinsic properties of fluorocarbon/hydrocarbon diblocks. These domains do not coalesce when compressed and survive beyond monolayer collapse. Formation of two-dimensional radial or ring-banded spherulites has also been observed. Fullsize Image
     
 
  • Yoshitaka Tsuchido, Ryota Abe, Megumi Kamono, Kimiya Tanaka, Makoto Ta ...
    2018 Volume 91 Issue 5 Pages 858-864
    Published: May 15, 2018
    Released: May 15, 2018
    JOURNALS RESTRICTED ACCESS

    Hydrosilylation of aromatic aldehydes and acetophenone with H2SiPh2 was studied by using Pt complexes as the catalyst. Reaction of aromatic aldehydes, such as PhCHO, 4-FC6H4CHO, 4-MeC6H4CHO and 4-CF3C6H4CHO with H2SiPh2 in the presence of [Pt(PPh3)3] catalyst proceeds smoothly at room temperature with similar reaction rates. The hydrosilylation of PhCHO with H2Si(C6H4-4-Me)2 proceeds faster than that with H2SiPh2. Comparison of the reactions of PhCHO with H2SiPh2 and with D2SiPh2 demonstrated a large kinetic isotope effect (3.1). The hydrosilylation of the aldehydes catalyzed by [Pt(PMe3)(μ-SiPh2)]3, reported in our previous paper, shows large dependence of the reaction rate on the aryl group of the substrate, in the order, 4-MeC6H4CHO ≫ PhCHO = 4-FC6H4CHO > 4-CF3C6H4CHO. Hydrosilylation of (3-vinyl)benzaldehyde and 10-undecenal in the presence of [Pt(PPh3)3] catalyst occurs at the carbonyl group selectively to form the corresponding alkoxysilanes. The hydrosilylation of acetophenone with H2SiPh2 catalyzed by [Pt(PPh3)3] forms 1-phenylethyl(diphenylsilyl)ether, while the reaction using the Pt3 catalyst is accompanied by dehydrosilylation to yield a mixture of the saturated and unsaturated silyl ethers.

feedback
Top