Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 88 , Issue 2
Showing 1-19 articles out of 19 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2010
  • Hiroko Tokoro, Shin-ichi Ohkoshi
    2015 Volume 88 Issue 2 Pages 227-239
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: October 15, 2014
    JOURNALS FREE ACCESS
    Since phase-transition phenomena in solid-state materials can change the magnetic, electrical, and optical properties with external stimuli, they are attracting widespread attention from the viewpoints of both fundamental science and practical applications. We have synthesized various cyano-bridged metal complexes possessing anomalous bistabilities that exhibit unprecedented phase transition phenomena. This paper focuses on rubidium manganese hexacyanoferrate, RbxMn[Fe(CN)6](x+2)/3·zH2O, which is a Prussian blue analogue. Here, the unique functionalities of rubidium manganese hexacyanoferrate are described: a charge-transfer-induced phase transition, control of the thermal hysteresis loop, and a huge thermal hysteresis with a hidden stable phase are presented as thermally-induced phase-transition phenomena, while a photoinduced phase collapse is described as a novel photoinduced phase-transition phenomenon. A one-shot-laser-induced charge-transfer phase transition is displayed as a photoinduced phase-transition phenomenon at ambient temperature. Moreover, second harmonic generation (SHG) and magnetization-induced second harmonic generation (MSHG) are provided as correlation effects between the optical and dielectrical properties. Finally, a one-shot-laser-induced photo-demagnetization and reversible photomagnetic switching between ferromagnetism and antiferromagnetism are demonstrated as photomagnetic effects.
    This paper focuses on the unique functionalities of rubidium manganese hexacyanoferrate: charge-transfer-induced phase transition, hidden substable phase, photoinduced phase collapse, photoinduced phase transition at ambient temperature, magnetization-induced second harmonic generation, one-shot-laser-induced photo-demagnetization, and reversible photomagnetic switching are described. Fullsize Image
     
The Chemical Society of Japan Award for Young Chemists for 2007
  • Shushi Suzuki
    2015 Volume 88 Issue 2 Pages 240-250
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: December 03, 2014
    JOURNALS FREE ACCESS
    Scanning probe microscopy (SPM) is widely used for analysis of structures on substrate surfaces. Particularly, scanning tunneling microscopy (STM) and noncontact atomic force microscopy (NC-AFM) enable real-space observations of solid surfaces at the atomic level with high spatial resolution. However, these microscopic measurement methods still involve difficulties in elemental analysis at the nanoscale for general purposes, although several validated solutions have already been proposed for well-defined cases. This brief review explains issues and their resolution, including topics related to the development of chemical analysis methodologies based on STM/NC-AFM, such as inelastic tunneling spectroscopy (IETS)-STM for spectroscopy of individual molecules, STM combined with synchrotron radiation X-ray sources for elemental analysis of surface structures, and force spectroscopy with atom tracking technology, as well as X-ray-aided noncontact atomic force microscopy (XANAM). Particularly, the review describes details of XANAM including recently obtained results on X-ray energy dependence of force spectroscopy and its two-dimensional recording as XANAM imaging, suggesting XANAM offers great potential to contribute to nanoscale investigations of chemical analysis for various purposes.
    The review describes details of XANAM including recently obtained results on X-ray energy dependence of force spectroscopy and its two-dimensional recording as XANAM imaging, suggesting XANAM offers great potential to contribute to nanoscale investigations of chemical analysis for various purposes. Fullsize Image
     
BCSJ Award Article
  • Tomoyuki Hamaguchi, Takuya Okamoto, Koji Mitamura, Kimihiro Matsukawa, ...
    2015 Volume 88 Issue 2 Pages 251-261
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 28, 2014
    JOURNALS FREE ACCESS
    We synthesized hydrophilic and hydrophobic carbon nanoparticles (CNPs) by femtosecond laser (0.8 µm, 40 fs) irradiation of the water layer of an aerated benzene/water (B/W) bilayer solution. Focusing intense femtosecond laser pulses onto water creates a high density of reactive species such as hydroxyl radicals in a well-confined volume; i.e., plasma filament. The properties of the particle surface were controlled simply by adjusting the laser focusing position, the duration between the preparation of B/W bilayer solution and the laser irradiation. The hydrophobic CNPs appeared to be nearly identical in size and morphology to hydrophilic CNPs. Raman spectroscopy revealed that both particles had a graphitic and disordered structure; however, IR spectroscopy clearly showed that the hydroxy group is the origin of the hydrophilicity. The time evolution of particle formation, products in water, and benzene dissolution behavior in water reveals that the surface properties are determined by the concentration of benzene in water. The diluted aqueous benzene solution gave hydrophilic particles; however, the density of particles was much smaller than that formed in B/W bilayer solution. We concluded that the production of denser hydrophilic CNPs in B/W bilayer was achieved by limiting the concentration of benzene in water layer by B/W interface, and by continuously supplying benzene into water layer through B/W interface. We discuss the subsequent reaction mechanism leading to CNPs of different surface characters.
    Hydrophilic and hydrophobic carbon nanoparticles were synthesized by femtosecond laser irradiation of an aerated benzene/water bilayer solution. The dense hydrophilic particle production was achieved by limiting the concentration of benzene in water and by continuously supplying benzene into water through the benzene/water interface. Fullsize Image
     
 
  • Masa-aki Sato, Syuhei Arita, Kazuki Kawajiri
    2015 Volume 88 Issue 2 Pages 262-270
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 17, 2014
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    Dihedral-angle-controlled 2,2′-bithiophenes with terminal ferrocenyl groups were designed and prepared as long π-conjugated systems. Electrochemical and spectroscopic studies were carried out to evaluate the one-electron-oxidized states of the diferrocenyl derivatives and the interaction between the two terminals. Oxidized diferrocenyl derivatives comprising a more flat bithiophene moiety showed electronic communication between both the terminal ferrocenyl moieties, while an oxidized diferrocenyl derivative comprising a distinctly twisted bithiophene moiety would exhibit only electrostatic communication (with no electronic communication). These results indicated that the interaction between the terminal ferrocene moieties is strongly affected by the twist in the π-conjugated system.
  • Takashi Sugimura, Satoshi Nakagawa, Naoya Kamata, Takahiro Tei, Takash ...
    2015 Volume 88 Issue 2 Pages 271-276
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 12, 2014
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    Reaction rate and enantioselectivity of asymmetric hydrogenation of methyl acetoacetate were studied over Raney nickel catalysts modified with (R,R)-tartaric acid, malic acid, or succinic acid to reveal the impacts of the modifier configuration. Catalysts comodified with two different acids were also examined to confirm the conclusions. From analysis of the enantiomer ratio of the hydrogenation product and initial reaction rate, tartaric acid (TA) was found to have dual functions as the modifier during the hydrogenation; effective suppression of the racemic catalysis on bare Ni surface and extensive enantiodifferentiating ligand acceleration by adsorbed TA. It was demonstrated that each adsorbed chiral modifier molecule independently takes part in the enantiospecific hydrogenation.
  • Ryoji Takahashi, Satoshi Kaneko, Shintaro Fujii, Manabu Kiguchi
    2015 Volume 88 Issue 2 Pages 277-282
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 14, 2014
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    We have investigated the photopolymerization of a photoresist on Au nanoparticles. Photopolymerization proceeded when samples were irradiated with light wavelengths longer than 480 nm. This was verified by IR spectroscopy and the presence of an interference pattern under visible light due to the formation of a polymerized film on the substrate. The progress of photopolymerization was not observed on flat Au or quartz plates without the Au nanoparticles. The photopolymerization region was extended from the nanoscale to macroscopic scale using a chemically amplified photoresist at elevated temperatures. The source intensity, wavelength, reaction temperature, and irradiation time-dependence measurements revealed that interactions between the resist and the Au nanoparticles modified the electronic structure of the resists, or electron transfer from through interband excitation of Au. These interactions subsequently lead to a red shift in the threshold wavelength of photopolymerization.
  • Shinji Toyota, Kan Wakamatsu, Takahiro Kawakami, Tetsuo Iwanaga
    2015 Volume 88 Issue 2 Pages 283-291
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 06, 2014
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    The structures and stabilities of 1,8-anthrylene cyclic oligomers having acetylene or diacetylene linkers were investigated by DFT calculations with M05 and M06 series functionals. The structures of the cyclic oligomers were reasonably reproduced at the M05-2X/6-31G* level by using the interlayer distance between stacking anthracene planes in the anthracene–acetylene cyclic tetramer as benchmark. The structural features of the cyclic oligomers ranging from dimers to hexamers were discussed on the basis of the optimized structures. The stabilities of the cyclic oligomers were analyzed by thermochemical calculations of the homodesmotic reactions. The decreased stabilities of the odd-numbered oligomers are mainly attributable to molecular strain due to bending deformations at acetylene carbons. The increased stabilities of the tetramers and the hexamers are attributable to the intramolecular π···π interactions between anthracene units. The contributions of other factors influencing the overall stability, such as conjugation, steric hindrance, aromaticity, and CH···π interaction, are also discussed.
  • Keisuke Kawamoto, Akio Ichimura, Hideki Hashimoto, Isamu Kinoshita, Ta ...
    2015 Volume 88 Issue 2 Pages 292-299
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 10, 2014
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    A series of potentially tridentate Schiff base ligands, {HOPhC=N-(CH2)3-XMe: X = S (HLSMe), Se (HLSeMe)}, was prepared by condensation reactions of salicylaldehyde and the corresponding functionalized propylamines. These ligands were used to form the monocationic complexes, [Mo3S4(LXMe)3]+ (X = S (1+), Se (2+)), through treatment of [Mo3S4(H2O)9]4+ with the appropriate Schiff base ligand in methanol. Single-crystal X-ray structural analysis of 1-PF6 revealed that one Schiff base ligand coordinates to each Mo via the O, N, and SMe donor atoms, and then the mono cationic cluster [Mo3S4(LSMe)3]+ has a pseudo C3 symmetry if the chirality around the coordinated sulfur atoms is not taken into account. Because of the arrangements of the asymmetric Schiff base ligand, this monocationic cluster possibly adopts one of two axial chiralities. Furthermore, each sulfur atom of the three coordinated SMe groups in the complex cation is also chiral affording the two enantiomers observed in the unit cell. Dynamic behaviors of complexes 1-PF6 and 2-PF6 in solution were examined using line shape analyses of variable temperature NMR spectra revealing that the rate constant of the chiral inversion at the S atoms in 1-PF6 is greater than that at the Se atoms in 2-PF6 and the difference in the ΔH values of 1-PF6 (47.1 kJ mol−1) and 2-PF6 (56.7 kJ mol−1) and the negative ΔS values (−39.9 and −57.5 J mol−1 K−1 for 1-PF6 and 2-PF6, respectively) suggest that the inversion processes involve bond cleavage between the metal centers and S or Se atoms followed by coordination of solvent molecules. The electrochemical properties of 1-PF6 and 2-PF6 were evaluated using cyclic voltammetry and this revealed that both 1+ and 2+ exhibit two consecutive, reversible one-electron reduction waves that are assigned to formal Mo(IV IV IV)/Mo(III IV IV) and Mo(III IV IV)/Mo(III III IV) couples, respectively. The ability of 1-PF6 and 2-PF6 to catalyze the electroreduction of H+ was also examined using CH3CO2H or CF3CO2H as a proton source. Noteworthy, the redox potentials for the catalytic wave depend on the acidity of the added acids. Thus, the catalytic current around the first reduction wave is observed in the presence of the stronger trifluoroacetic acid as a proton source, while the current around the second reduction wave appears when the weaker acetic acid is used.
  • Kengo Nakai, Tomonori Misaki, Yasuaki Okamoto, Takashi Sugimura
    2015 Volume 88 Issue 2 Pages 300-302
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 20, 2014
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    Asymmetric hydrogenation of α-phenylcinnamic acid catalyzed by cinchonidine (CD)-modified palladium has been performed. Without benzylamine (BA), a modification inconsistency was observed: the rate diminished when a small amount of CD was used, whereas the product enantiomeric excess (ee) increased when substantially more CD was used. By altering the amount of amine additive, we deduced that this inconsistency was caused by the amine effect of CD itself. With a 1,8-diazabicyclo[5.4.0]undec-7-ene additive, the catalytic amount was sufficient to result in the highest ee of 81%.
  • Yoshinori Hirata
    2015 Volume 88 Issue 2 Pages 303-307
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: December 02, 2014
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    We have measured the polarized absorption and picosecond transient absorption spectra of trans-stilbene in poly(vinyl alcohol) (PVA) films. We found that the dichroic ratio in the first absorption band and the lifetime of the S1 state increased as the hold-time was increased. The hold-time is the duration in which sample films were kept wet before they were dried. For similar values of the hold-time, the absorption spectra showed a red shift and slight sharpening. These results indicate that during the hold-time, solute–polymer interactions become strong; these interactions not only act as the orienting force during film stretching but also act as friction that opposes isomerization.
  • Carolina Infante-Rodriguez, Lisianne Domon, Pascal Breuilles, Daniel U ...
    2015 Volume 88 Issue 2 Pages 308-326
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 26, 2014
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    The crystalline sulfone 18 (X-ray analysis), prepared from the monoacetate product [i.e., (+)-12; 98.2% ee] of the lipase PS-catalyzed acetylation of anti,anti-2,4-dimethyl-1,3,5-pentantriol (19a), has been elaborated either to crocacin C (10) or stigmatellin (1), thereby providing a convenient divergent access to these two natural antibiotics.
  • Eiji Nakata, Yoshijiro Nazumi, Yoshihiro Yukimachi, Yoshihiro Uto, Hit ...
    2015 Volume 88 Issue 2 Pages 327-329
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 21, 2014
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    A fluorescent nanoprobe was designed based on self-assembled seminaphthorhodafluor (SNARF) derivatives (SNARF-OTBDPS) to detect the fluoride ions present in aqueous solutions. The tert-butyldiphenylsilyl (TBDPS) group in SNARF-OTBDPS showed good stability against hydrolysis by forming self-assembled clusters and retained good selectivity towards fluoride ions in aqueous solution.
  • Yuhi Inada, Toru Amaya, Akinori Saeki, Shu Seki, Toshikazu Hirao
    2015 Volume 88 Issue 2 Pages 330-332
    Published: February 15, 2015
    Released: February 15, 2015
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    Laser-induced carbonization of fullerene C60, sumanene derivatives, and triphenylene was studied from a view point of exposure-time dependence of time-resolved microwave conductivity (TRMC). Their increased rate of TRMC decreased in the order above.
  • Ilya D. Gridnev, Andrey Kh. Vorobiev
    2015 Volume 88 Issue 2 Pages 333-340
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 21, 2014
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    Recent observation of the acetal species in the course of autoamplifying Soai reaction was analysed by the formal kinetic analysis of the experimental data and DFT computations. Kinetic analysis demonstrated convincingly that the observed species cannot be a precursor of the reaction product. Hence, it is an off-loop species that is not important for the process of the chirality amplification. DFT search for a kinetically stable acetal species resulted in the location of a Zn3 cluster stabilized with three Zn–O–Zn bridges.
  • Anirban Das, Yoshio Takahashi, Asuka Tanaki
    2015 Volume 88 Issue 2 Pages 341-345
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: November 28, 2014
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    A study using X-ray absorption fine structure (XAFS) spectroscopy in conjunction with chemical analyses was undertaken to determine the form of lead (Pb) compound(s) used as additives in plastic bags. Comparison of Pb LIII-edge X-ray absorption near-edge structure (XANES) in samples with those of the standards, and XANES simulation studies revealed that spectra of samples were almost identical to that of PbCrO4, and ca. 80% of Pb was present in the form of PbCrO4. These findings were supported by the facts that Cr-XANES spectra of samples resembled that of PbCrO4, and Cr/Pb molar ratios in samples calculated from simulation of XANES agreed reasonably well with those of the chemical data. Results of k3-weighted extended X-ray absorption fine structure (EXAFS) spectra of three of the samples showed that they resembled that of the PbCrO4.
  • Yuichi Kitagawa, Shin Ogasawara, Daisuke Kosumi, Hideki Hashimoto, Hit ...
    2015 Volume 88 Issue 2 Pages 346-351
    Published: February 15, 2015
    Released: February 15, 2015
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    Since photochemical CO2 reduction using long wavelength regions of sunlight is important, we have reported the first photochemical CO2 reduction with red visible light (>650 nm) by using a synthetic chlorophyll derivative covalently linked with a rhenium bipyridine complex. In the reported system, electron/energy transfer from the photoexcited chlorophyll to the catalytic Re complex was not so effective. To accelerate the process for achieving efficient photochemical reduction of CO2, we controlled the redox potential of Re complex and improved the chlorophyll donor by a simple modification. As a result, we achieved strong quenching of the excited states of a 131-deoxochlorophyll derivative with a rhenium bipyridine complex in a molecule.
  • Jahar Dey, Koel Biswas, Uttam Thapa, Santaram Joshi, Ibapalei Shisha K ...
    2015 Volume 88 Issue 2 Pages 352-357
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: December 01, 2014
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    We demonstrate a facile method for the synthesis of silver nanoparticles (Ag NPs) by using silver nitrate (AgNO3) as precursor, p-toluidine as reducing agent and cetyltrimethylammonium bromide (CTAB) as capping agent. The main highlight of the present synthesis is the formation of NPs at near neutral pH. The effect of the concentrations of precursor, reducing agent and capping agent, and of pH on the stability and size of the NPs has been studied using UV–vis spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM) techniques. Critical concentrations of AgNO3, reducing agent and CTAB required for the synthesis of Ag NPs are found to be 0.002 mol dm−3. The NPs prepared have been tested for antibacterial properties for a series of bacteria and they are found to have good antibacterial efficacy. In combination with some commercially available antibiotics, synergism in the antibacterial activity of the NPs has also been observed.
  • Masahiro Saeki, Kotaro Dai, Shuhei Ichimura, Yoshinori Tamaki, Kazuaki ...
    2015 Volume 88 Issue 2 Pages 358-365
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: December 01, 2014
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    A series of [Ni(dmit)2] (dmit: 1,3-dithiole-2-thione-4,5-dithiolate) complex salts of benzyldimethyl(ω-phenylalkyl)ammonium cation (BnCnPh: n represents the alkylene chain length; n = 1–4) have been prepared and characterized by X-ray crystallographic structural analysis. All complex salts were found to be composed of alternant stacks of layers of [Ni(dmit)2] anion dimers and cations (Layer I), and isolated cation layers (Layer II). In BnC3Ph complex salt, polymorphs, P1 (α-form) and P2(1)/c (β-form) crystals are obtained from similar crystallizing conditions. One of the biggest structural differences is the arrangement of [Ni(dmit)2] anion dimers; herringbone in α-form, while nearly parallel in β-form. Other BnCnPh complex salts adopt herringbone structure. Interestingly, BnCnPh series (n = 1, 2, 3α, 4) exhibit three types of pronounced odd–even effect in the crystal structures; 1. Dihedral angles between the two kinds of terminal phenyl groups, 2. Angles between [Ni(dmit)2] anion dimers, and 3. Ni–N+ distances. Such a structural feature is a consequence of the bulkiness of cation involving two phenyl groups. Introduction of terminal phenyl group is concluded to have increased the steric effect and led to the formation of the novel crystal structure of [Ni(dmit)2] complex salts.
  • Naoyuki Shibayama, Hironobu Ozawa, Yousuke Ooyama, Hironori Arakawa
    2015 Volume 88 Issue 2 Pages 366-374
    Published: February 15, 2015
    Released: February 15, 2015
    [Advance publication] Released: December 04, 2014
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    Cosensitized plastic-substrate dye-sensitized solar cells (PDSCs) with Black dye and a pyridine-anchor organic dye (NI5 or YNI-2) have been prepared to improve conversion efficiency. Detailed analysis of light-harvesting efficiency spectra and ATR-IR spectra of the cosensitized TiO2 photoelectrodes revealed that the amount of pyridine anchor dye, which adsorbs to the Lewis acid sites of the TiO2 surface and works as a sensitizer, increased with prolonging the immersion time of the Black-dye-adsorbed TiO2 photoelectrodes into the dye-adsorption solvent of pyridine anchor dye up to 60 min. In addition, these measurements also revealed that the dye aggregation between Black dye and pyridine anchor dye occurred just after immersion, even though the amount of pyridine anchor dye which forms dye aggregation with Black dye is small when the immersion time is shorter than 30 min. The conversion efficiency of the Black-dye-based PDSC was improved by cosensitization with pyridine anchor dyes up tol 30 min immersion, and it decreased largely when the immersion time is extended to 60 min. A conversion efficiency of 8.3% (AM 1.5, 100 mW cm−2), which is the highest conversion efficiency in the PDSCs, could be achieved in the cosensitized PDSC with Black dye and NI5 prepared under the optimized conditions.
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