Performance information

• Thermoreversible helical fibers from photoreactive triphenylene-derived liquid crystals in liquid paraffin.　　　　　　　　　　　　　　　
  Takuji Hirose; Yuka Kikuchi; Tomoaki Nakano; Tsukasa Ohno; Kengo Kawamura; Normazliana Binti Nazri; Atsuhiro Fujimori; Koichi Kodama; Mikio Yasutake
  Heliyon, Volume：9, Number：11, First page：e22037, Nov. 2023, ［International magazine］
  Liquid crystalline triphenylene derivatives, TPC1p-n (n = 6, 12, 14, 16) were prepared using p-alkoxycinnamate as the [2+2] photo-cyclization site. TPC1p-n (n = 12, 14, 16) showed Colr phase and gave crescent-shaped or helical fibers after UV-irradiated in liquid paraffin solutions at 90 and 110 °C in the Colr temperature range. The apparent photoreaction products were shown to be thermally reversible, i.e. they dissolved in liquid paraffin at high temperatures and reappeared on cooling, indicating that they were aggregates of oligomerized TPC1p-n. The reaction mechanism was discussed in terms of the structure of the liquid crystalline phase.
  English, Scientific journal
  DOI：https://doi.org/10.1016/j.heliyon.2023.e22037
  DOI ID：10.1016/j.heliyon.2023.e22037, PubMed ID：38053870, PubMed Central ID：PMC10694167
• Rack-gear structures in columnar liquid crystal phases of trialkoxybenzyl pentafluorobenzoates and their influences on intercolumnar interdigitation and macroscopic morphologies　　　　　　　　　　　　　　　
  Keiki Kishikawa; Hiromoto Nakagomi; Masaya Masuda; Yuto Suda; Ryuji Ushiki; Mikio Yasutake; Michinari Kohri; Tatsuo Taniguchi
  LIQUID CRYSTALS, Volume：50, Number：2, First page：319, Last page：330, Jan. 2023
  In this study, 3,4,5-trialkoxybenzyl pentafluorbenzoates with alkyl chains of various lengths were synthesised, and the phase transition behaviours, liquid crystallinities, and molecular packing structures of their columnar phases were investigated. The results showed that discs comprising two half-discoid molecules stack up to form columns with rack-gear structures, generating columnar liquid crystal phases. From powder and single crystal X-ray diffraction investigation, the mechanism of the self-assembly of molecules into columns and their intercolumnar interdigitation was postulated. Furthermore, it was revealed that the combination of alkyl groups of the benzyl groups was closely related to the type of columnar liquid crystal phases generated and the macroscopic morphologies of the liquid crystal domains.
  TAYLOR & FRANCIS LTD, English, Scientific journal
  DOI：https://doi.org/10.1080/02678292.2022.2142884
  DOI ID：10.1080/02678292.2022.2142884, ISSN：0267-8292, eISSN：1366-5855, Web of Science ID：WOS:000881870800001
• Electrochemical Properties and Electrochromism of 6-Aryl-1,3-bis(trimethylsilyl)fulvenes and Their Derivatives.　　　　　　　　　　　　　　　
  Ryota Tatemura; Mikio Yasutake; Hidenori Kinoshita; Katsukiyo Miura
  The Journal of organic chemistry, Volume：87, Number：1, First page：172, Last page：183, Jan. 2022, ［International magazine］
  In this study, we have disclosed intriguing electrochromic properties of 6-aryl-1,3-bissilylfulvenes. The electrolyte solutions (0.1 M n-Bu4NClO4 in acetonitrile or dichloromethane) of some 6-aryl-1,3-bissilylfulvenes showed notable color changes when superimposed negative voltages were applied to the solutions. Investigation of the substituents at position 6 revealed that the solution of 1,3-bissilyl-6-anthracenylfulvene exhibited chromic changes under both applied superimposed negative and positive voltages and exhibited a three-color electrochromism. Electrochromic properties of 1,6-diarylfulvenes derived from 6-aryl-1,3-bissilylfulvenes were also investigated. The aryl group at position 1 also contributed to the electrochromism of fulvenes.
  English, Scientific journal
  DOI：https://doi.org/10.1021/acs.joc.1c02133
  DOI ID：10.1021/acs.joc.1c02133, PubMed ID：34913709
• Discotic liquid crystals of transition metal complexes 58^†: Novel phthalocyanine-based mesogenic monomers and polymers exhibiting spontaneous homeotropic alignment and helical tetragonal columnar structure　　　　　　　　　　　　　　　
  Ayumi Suzuki-Ichihara; Makiko Sugibayashi-Kajita; Masahiro Ariyoshi; Mikio Yasutake; Kazuchika Ohta
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：25, Number：9, First page：800, Last page：817, Sep. 2021
  Two synthetizations of a novel series of phthalocyanine-based discotic liquid crystals substituted by a polymerizable group, acryloyl group or a norbornene group: 2-(12-acryloyloxydodecyloxy)-3-methoxy-9,10,16,17,23,24-hexalcis (3,4-dialkoxyphenoxy)phthalocyaninato copper(II) [abbreviated as (n,12)PcCu(OCH3)(Acryloyl) (7: e (n = 10), f (n = 12), g (n = 14))] and 2-(12-norborn-2-enecarbonyloxydodecyloxy)-3-methox y-9,10,16,17,23,24- hexalcis(3,4-dialkoxyphenox y)-phthalocyaninato copper(II): [abbreviated as (n, 12)PcCu(OCH3)(Norb) (9e, f, g)]. Their liquid crystalline properties and homeotropic alignment were investigated using a polarizing microscope, a differential scanning calorimetry (DSC), and a temperature-variable X-ray diffractometer. As a result, each of the derivatives gave a Col(tet), mesophase in the higher temperature region, displaying perfect homeotropic alignment between the two glass plates. In order to obtain the thin film while keeping their homeotropic alignment at room temperature, attempts to polymerize the monomers, 7 and 9, in the Col(tet), phase showed homeotropic alignment. The polymerization of the acryloyl-substituted monomers (7) was not successful in any of the methods, whereas the polymerization of norbornene-substituted monomers (9) was quite successful by ring-opening metathesis polymerization with a Grubbs catalyst to obtain the novel polymers, poly-(n, 12)PcCu(OCH3)(Norb) (10e, f, g). Each of the polymers (10) were found to show a perfect homeotropic alignment from room temperature to ca. 200 degrees C of the decomposition temperature. Moreover, it was also revealed from temperature-variable small-angle X-ray diffraction studies that each of the polymers 10 showed a helical Col(tet), (helical tetragonal columnar) structure. The helical Col(tet), phase structure may be able for use in organic electroltuninescent devices and solar cells in the future.
  WORLD SCIENTIFIC PUBL CO PTE LTD, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424621500498
  DOI ID：10.1142/S1088424621500498, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000700303200003
• Discotic liquid crystals of transition metal complexes 59: Parity effect of the number of d-electrons on the columnar mesomorphism and homeotropic alignment of 1,4-diazatriphenylenocyaninato metal(II) complexes　　　　　　　　　　　　　　　
  Masahiro Shichi; Mikio Yasutake; Kazuchika Ohta
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：25, Number：9, First page：843, Last page：857, Sep. 2021
  Twenty super-discotic liquid crystals based on a largely expanded pi-conjugated macrocycle of 1,4-diazatriphenylenocyaninato metal(II) complex, (abbreviated as (CnO)(16) TzM: M = Co(1), Ni(2), Cu(3), Zn(4); n = 8(a), 10(b), 12(c), 14(d), 16(e)) were synthesized in order to investigate their mesomorphism and homeotropic alignment properties by using polarization microscopic observations, differential calorimetry, thermogravimetry, and temperature-variable X-ray diffraction. As a result, the (CnO)(16)TzCo and (CnO)(16)TzCu complexes with an odd number of d-electrons in the central metal ions showed a tetragonal columnar (Col(tet)) mesophase for n = 8 similar to 14, which exhibit spontaneous homeotropic alignment for a very wide temperature range from rt to the decomposition temperature at around 340 degrees C. On the other hand, the (CnO)(16)TzNi and (CnO)(16)TzZn complexes with an even number of d-electrons in the central metal ions showed a rectangular columnar (Col(r)(P2(1)/a())) mesophase for n = 8 similar to 16, which did not exhibit homeotropic alignment. As far as is known, such a unique parity effect of the number of d-electrons on mesomorphism accompanied by homeotropic alignment has never been reported to date.
  WORLD SCIENTIFIC PUBL CO PTE LTD, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424621500668
  DOI ID：10.1142/S1088424621500668, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000700303200007
• Discotic liquid crystals of transition metal complexes 57^†: X-ray diffraction halo jumps originated from sudden free rotation of substituent groups to induce mesomorphism　　　　　　　　　　　　　　　
  Takahiro Nishiguchi; Kouki Sugiyama; Hiromu Nakamura; Mikio Yasutake; Kazuchika Ohta
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：24, Number：4, First page：563, Last page：576, Apr. 2020
  We have synthesized a novel series of four flying-seed-like liquid crystals (1Ph-PhO)(4)PcM [5-M: M = Co (5-Co), Ni (5-Ni), Cu (5-Cu) and Zn (5-Zn)] which are based on a phthalocyanine core having peripheral bulky groups without long alkyl chains, in order to clarify the precise mechanism inducing their mesomorphism. For comparison, we have also synthesized a long alkyl-chain-substituted liquid crystal (m-C20OPhO)(8)PcCu (7o) having the same phthalocyanine core with long alkyl chains in the periphery. Each of the derivatives 5-M and 7o showed a hexagonal ordered columnar (Col(ho)) mesophase. Very interestingly, the halo positions in the X-ray diffraction patterns for the Col(ho) mesophases of the flying-seed-like liquid crystals 5-M and the long alkyl-chain-substituted liquid crystal 7o were quite differently given at 5.7-6.2 angstrom and 4.6-4.7 angstrom, respectively. The halo positions of the representative derivatives 5-Cu and 7o having the same copper phthalocyanine (PcCu) core were finely measured at various temperatures by using the temperature-variable small angle X-ray diffraction technique. As the result, the derivatives 5-Cu and 7o showed sudden jumps of halo position from 5.5 to 5.7 angstrom and from 4.2 to 4.6 angstrom, respectively, at the phase transition from the crystalline phase to the liquid crystalline phase (Col(ho)). This means that the volume changes (Delta V) corresponding to these halo jumps originate from two different kinds of mechanisms by sudden free rotation of the bulky substituents and by sudden melting of the long alkyl chains. Thus, in this work we have unambiguously clarified these two different mechanisms inducing mesomorphism.
  WORLD SCI PUBL CO INC, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424620500042
  DOI ID：10.1142/S1088424620500042, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000522812700007
• Polymeric fibers and microporous films by photo-crosslinking of triphenylene-derived liquid crystals　　　　　　　　　　　　　　　
  Takuji Hirose; Zhe Xu; Yuka Kikuchi; Masahito Fukushima; Kengo Kawamura; Yosuke Kaguchi; Koichi Kodama; Mikio Yasutake
  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, Volume：57, Number：5, First page：605, Last page：612, Mar. 2019
  Two series of photoreactive discotic liquid crystals consisting of a triphenylene core and six cinnamate units with one (TPC1(n)) or two (TPC2(n)) n-alkoxy groups (CnH2n+1O; n = 10-14), respectively, as peripheral groups are synthesized. Both of them are polymerized into fibers up to 2 mm long by UV irradiation in liquid paraffin in the columnar LC temperature ranges. The fiber structures seem to be preconstructed in liquid paraffin. In addition, TPC2(n) are shown to form microporous films up to 15 mu m in diameter by simply casting the solutions of some solvents followed by drying for several minutes in air at room temperature. Photoirradiation of the films in the LC temperature range converts them to polymeric ones while preserving the microporous and hexagonally ordered structure. From comparison with TPC1(n) and the hydrogenated derivative of TPC2(12), the porous film-forming property is suggested to result from the combination of the double bond of the cinnamoyl group and the two long alkoxy chains on the phenyl ring. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 605-612
  WILEY, English, Scientific journal
  DOI：https://doi.org/10.1002/pola.29299
  DOI ID：10.1002/pola.29299, ISSN：0887-624X, eISSN：1099-0518, Web of Science ID：WOS:000456602400004
• Discotic liquid crystals of transition metal complexes 56⁺: Synthesis of mesogenic phthalocyanine-fullerene dyads and influence of the substitution position of alkoxy chains and the kind of terminal groups on appearance of the helical supramolecular structure　　　　　　　　　　　　　　　
  Kohei Ishikawa; Ayumi Watarai; Mikio Yasutake; Kazuchika Ohta
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：22, Number：8, First page：693, Last page：715, Aug. 2018
  We have synthesized twelve novel discotic columnar liquid crystals based on a phenoxy-group-substituted phthalocyaninato copper(II) complex having the same alkoxy chain of C16H33O at different positions in the phenoxy group: the parent compounds {0a similar to 0c-16} and the OH-substituted compounds {3a similar to 3c-16}, the OFBA-substituted compounds {2a similar to 2c-16} and the C-60-substituted dyads {1a similar to 1c-16}. The letters of a, b and c mean substitution positions of C16H33O group at m-, p-and m, p-, respectively. We have investigated the influence of both substitution position of the alkoxy chains and the kind of terminal groups (OH, OFBA and C-60) on the mesomorphism and the helical supramolecular structure, by using DSC, POM and temperature-variable small angle X-ray diffraction measurements. As a result, an additional big peak (Peak H) tends to appear at around 2 theta = 1.1 degrees in the X-ray diffraction patterns only for the dyads {1a similar to 1c-16} but not for the other compounds, {0a similar to 0c-16}, {3a similar to 3c-16} and {2a similar to 2c-16}, regardless of the substitution positions of the alkoxy group. Moreover, we revealed that both the m-substituted derivative 1a-16 and the m, p-substituted derivative 1c-16 gave Peak H, but that only the p-substituted derivative 1b-16 did not give Peak H among these three dyads {1a similar to 1c-16}. From the temperature-variable small angle X-ray diffraction measurements for the m, p-substituted derivative 1c-16 using two different sample preparation methods, we proved that the Peak H originates from a helical pitch of fullerenes. We also pointed out that the m-substituted long alkoxy chains are at least needed to form the helical supramolecular structure in the present (PhO)(6)PcM-C-60-based dyads.
  WORLD SCI PUBL CO INC, English, Scientific journal
  DOI：https://doi.org/10.1142/S108842461850092X
  DOI ID：10.1142/S108842461850092X, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000440658500009
• Discotic liquid crystals of transition metal complexes, 55⁺: Novel chlorine-substituted phthalocyanine derivatives showing mesomorphism and low HOMO energy level　　　　　　　　　　　　　　　
  Masashi Yatabe; Akio Kajitani; Mikio Yasutake; Kazuchika Ohta
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：22, Number：1-3, First page：32, Last page：45, Jan. 2018
  We have synthesized a series of novel phthalocyaninato copper(II) (abbriviated as PcCu) compounds, 1,4,8,11,15,18,22,25-octakisalkoxy-2,3,9,10,16,17,23,24-octachloro-phthalocyaninato copper(II) (abbreviated as (alpha-CnO)(8)(beta-Cl )(8)PcCu (4a-4d): n = 6 (a), 8 (b), 10 (c) and 12 (d)) and, for comparison, another series of PcCu compounds, 1,4,8,11,15,18,22,25-octakisalkoxyphthalocyaninato copper(II) (abbreviated as (alpha-CnO)(8)PcCu (1a-1d)). The PcCu derivatives 1a-1d are substituted by alkoxy chains only at the a positions (1,4,8,11,15,18,22,25). On the other hand, the PcCu derivatives 4a-4d are substituted by alkoxy chains at the alpha positions and chlorine atoms at the beta positions (2,3,9,10,16,17,23,24). We have investigated the influence of chlorine atoms substituted at the beta positions of the Pc ring on mesomorphism, spectroscopic and electronic properties for these two series of PcCu derivatives 1 and 4 by using a polarizing optical microscope, DSC, temperature-variable small angle X-ray diffractometer, a UV-Vis spectrophotometer and cyclic voltammetry. Each of the derivatives 1a-1d is crystalline without showing mesomorphism. On the other hand, each of the chlorine-substituted PcCu derivatives 4a-4d shows plural phase transitions, and the longer chain-substituted PcCu derivatives 4c-4d show a rectangular ordered columnar [Col(ro)(P2m)] mesophase. Furthermore, we have revealed that each of the PcCu derivatives 4a-4d shows a Q-band in the near-infrared region and a lower HOMO energy level than conventional phthalocyanine derivatives.
  WORLD SCI PUBL CO INC, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424617500717
  DOI ID：10.1142/S1088424617500717, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000427932100005
• Development of Liquid Crystal Materials Having an Anthraquinone and Bithiophene Moieties, and Their Electrochromic Properties　　　　　　　　　　　　　　　
  Mikio Yasutake; Masahiro Takatsudo; Takuya Tamura; Kana Yamada; Tsubasa Kamiya; Takuji Hirose
  ELECTROCHEMISTRY, Volume：85, Number：12, First page：768, Last page：774, Dec. 2017, [Reviewed]
  Three kinds of liquid crystalline compounds (AQBD1, AQBD2 and AQBT) having an anthraquinone and a bithiophene moieties were synthesized. The mesophases have been characterized by polarized optical microscopy (POM) observation, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) studies. AQBD1 and AQBT were determined to form colomnar phases while AQBD2 showed a smectic phase. The disc units of the columnar phases of AQBD1 and AQBT were expected to contain 2 and 3 molecules, respectively. The electrochemical properties of AQBT, which keeps the liquid crystalline phase at room temperaure, were examined by cyclic voltammetry (CV) and optoelectrochemical measurements. The reversible electrochemical response of AQBT was confirmed in solution. The reversible color change of EC device prepared from liquid crystalline AQBT (LC-AQBT) was also observed at room temperaure and the positive potentials, which is due to the bithiophene unit. (C) The Electrochemical Society of Japan, All rights reserved.
  ELECTROCHEMICAL SOC JAPAN, Japanese, Scientific journal
  DOI：https://doi.org/10.5796/electrochmistry.85.768
  DOI ID：10.5796/electrochmistry.85.768, ISSN：1344-3542, Web of Science ID：WOS:000418110300001
• Phthalocyanine-based discotic liquid crystals switching from a molten alkyl chain type to a flying-seed-like type　　　　　　　　　　　　　　　
  Hiromu Nakamura; Kouki Sugiyama; Kazuchika Ohta; Mikio Yasutake
  JOURNAL OF MATERIALS CHEMISTRY C, Volume：5, Number：29, First page：7297, Last page：7306, Aug. 2017
  We have synthesised a series of phthalocyanine-based discotic liquid crystals, (m-CnOPhO)(8)PcCu (n = 1-20: 2a-o), and investigated their mesomorphism by using a polarizing optical microscope (POM), a differential scanning calorimeter (DSC) and a temperature-dependent small angle X-ray diffractometer. We found that each of the derivatives 2a-o shows mesomorphism. However, the mesomorphism of the (m-CnOPhO)(8)PcCu derivatives strongly depends on the alkoxy chain length (n). The mesomorphism of the short chain-substituted derivatives 2a-e for n = 1-5 is a flying-seed-like type induced by flip-flop of the peripheral bulky substituents, whereas the mesomorphism of the long chain-substituted derivatives 2j-o for n = 10-20 is a conventional molten alkyl chain type induced by melting of the long alkyl chains. The moderately long chain derivatives (2f-i) for n = 6-9 in between show both types of mesophases. The detailed temperature-dependent X-ray diffraction measurements were carried out for three representative derivatives, 2b (n = 2 for n = 1-5), 2h (n = 8 for n = 6-9), and 2o (n = 20 for n = 10-20). As a result, we revealed that the Col(ro)(P2m) mesophase in 2b (n = 2) gave a halo denoted as Halo(arom). at d congruent to 5.2 angstrom due to flip-flop of the bulky aromatic substituents, and that the Colho mesophase in 2o (n = 20) gave a halo denoted as Halo(alkyl) at d congruent to 4.6-4.8 angstrom due to melting of the long alkyl chains. Therefore, we can distinguish the type of mesophase from Halo(arom). and Halo(alkyl). Very interestingly, the (m-C8OPhO)(8)PcCu (2h) derivative having moderately long alkyl chains gave Halo(alkyl) at about 4.8 angstrom in the lower temperature mesophase of Col(ho), but Halo(arom). at about 5.2 angstrom in the higher temperature mesophase of Col(ro)(P2(1)/a). This means that melting of the alkyl chains induces the Col(ho) phase in the lower temperature region, but that flip-flop of the bulky aromatic substituents induces the Col(ro)(P2(1)/a) phase in the higher temperature region. This unusual reverse phase transition sequence from a higher symmetry of the Col(h) mesophase to a lower symmetry of the Col(r) mesophase on a heating stage is attributable to such a unique stepwise melting of these two different types of substituents. To the best of our knowledge, this mesogen (2h) is the first example switching mesomorphism from the molten alkyl chain type to the flying-seed-like type in a discotic liquid crystal.
  ROYAL SOC CHEMISTRY, English, Scientific journal
  DOI：https://doi.org/10.1039/c7tc01197k
  DOI ID：10.1039/c7tc01197k, ISSN：2050-7526, eISSN：2050-7534, Web of Science ID：WOS:000406376000020
• Discotic liquid crystals of transition metal complexes, 53: synthesis and mesomorphism of phthalocyanines substituted by m-alkoxyphenylthio groups　　　　　　　　　　　　　　　
  Yoshiaki Chino; Kazuchika Ohta; Mutsumi Kimura; Mikio Yasutake
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：21, Number：3, First page：159, Last page：178, Mar. 2017
  We have successfully synthesized a series of novel octakis(m-alkoxyphenylthio) phthalocyaninato copper(II) complexes, (m-CnOPhS)(8)PcCu (n = 2, 4, 6, 8, 10, 12, 14, 16: 1b similar to 1i), by our developed method to reveal their mesomorphism. The phase transition behavior and mesophase structures have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. Interestingly, the very short chain-substituted derivatives, (m-C1OPhS)(8)PcCu (1a) and (m-C2OPhS)(8)PCu (1b), show a hexagonal ordered columnar (Col(ho)) mesophase, whereas each of the other longer-chain-substituted derivatives, (m-CnOPhS)(8)PcCu (n = 4 similar to 16: 1c similar to 1i), shows only rectangular ordered columnar (Col(ro)) mesophase(s). In contrast to the present longer-chain-substituted phenylthio derivatives, each of the previous longer-chain-substituted phenoxy derivatives, (m-CnOPhO)(8)PcCu (n = 10-20), shows a different columnar mesophase of Colho. We discuss this difference of mesomorphism from the viewpoint of the different steric hindrance originated by the peripheral substituents, PhO and PhS groups. Moreover, we could estimate the optical band gaps of (m-C10OPhO)(8)PcCu and (m-C10OPhS)(8)PcCu (1f) from absorption edge of the Q-bands to be 1.79 eV and 1.70 eV, respectively. Therefore, the phenylthio-substituted derivative gave a narrower band gap by ca. 0.1 eV in comparison with the phenoxy-substituted derivative.
  WORLD SCI PUBL CO INC, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424617500389
  DOI ID：10.1142/S1088424617500389, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000404984300001
• Flying-seed-like liquid crystals 7(+): Synthesis and mesomorphism of novel octakis(m-chloropyridyloxy) phthalocyanato copper(II) complexes　　　　　　　　　　　　　　　
  Kazuchika Ohta; Kaori Adachi; Mikio Yasutake
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：21, Number：1, First page：48, Last page：58, Jan. 2017, [Reviewed]
  We have synthesized three novel octakis(m-chloropyridyloxy) phthalocyaninato copper(II) complexes, [x-PyO(m-Cl)](8)PcCu(x = 2, 3, 4: 2a-2c), keeping a chlorine atom at the meta position on the 2-, 3- and 4-pyridyloxy group, in which the nitrogen atom is located at the 2-, 3-and 4-positions, respectively. Their phase transition behavior and the mesophase structure have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. Very interestingly, the mesomorphism appears with strong dependence of the position of nitrogen in m-chloropyridyloxy group. The derivative [3-PyO(m-Cl)](8)PcCu (2b) introduced a nitrogen atom at the 3-position is not mesogenic but crystalline. On the other hand, the derivative [2-PyO(m-Cl)](8)PcCu (2a) introduced a nitrogen atom at the 2-position shows columnar mesomorphism only at very high temperatures over 325 degrees C. The derivative [4-PyO(m-Cl)](8)PcCu (2c) introduced a nitrogen atom at the 4-position shows columnar mesomorphism in a very wide temperature region from rt to the decomposition temperature at 306 degrees C. From the viewpoint of N center dot center dot center dot Cl halogen bond, we have discussed about relationship between their mesomorphism and the position of nitrogen atom in m-chloropyridyloxy group.
  WORLD SCI PUBL CO INC, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424617500043
  DOI ID：10.1142/S1088424617500043, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000396390700007
• Discotic liquid crystals of transition metal complexes 52: Synthesis and homeotropic alignment of liquid crystalline phthalocyanine-fullerene dyad bridged by vanillin　　　　　　　　　　　　　　　
  Ayumi Watarai; Kazuchika Ohta; Mikio Yasutake
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：20, Number：12, First page：1444, Last page：1456, Dec. 2016, [Reviewed]
  We have synthesized a novel liquid crystalline phthalocyanine(Pc)-fullerene(C-60) dyad (C14S)(6)PcCu-VAN-C-60 (3a) bridged by an inexpensive natural product of vanillin (VAN), instead of the previous long n-alkylene chain spacer. We have also synthesized a comparative dyad (C14S)(6)PcCu-OPh-C-60 (3b) bridged by p-hydroxybenzaldehyde (OPh), in order to investigate the influence of the methoxy group in the vanillin moiety on homeotropic alignment between two glass plates. Very interestingly, homeotropic alignment could be observed only for the dyad (C14S)(6)PcCu-VAN-C60 (3a) having a methoxy group in the vanillin moiety, whereas it could not be observed for the dyad (C14S)(6)PcCu-OPh-C-60 (3b) having no methoxy group at the phenoxy group. It is very noteworthy that such a slight difference in these molecular structures between 3a and 3b becomes a crucial point to show the homeotropic alignment. Each of the dyads, 3a and 3b, showed two hexagonal ordered columnar (Col(ho)) mesophases. Each of the Col(ho) mesophases in 3a and 3b gave an additional very strong reflection peak named as Peak H in a very low angle region of the SAXS (small angle X-ray scattering) pattern. Peak H could be established, from two different SAXS measurement methods, as one pitch in a helical structure of the fullerenes around the Pc column.
  WORLD SCI PUBL CO INC, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424616501194
  DOI ID：10.1142/S1088424616501194, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000393046400005
• Flying-seed-like mesogens 6: Synthesis and mesomorphism of phthalocyanine derivatives substituted by pentafluorosulfanylphenoxy group　　　　　　　　　　　　　　　
  Ayumi Watarai; Kazuchika Ohta; Mikio Yasutake
  JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, Volume：20, Number：7, First page：822, Last page：832, Jul. 2016
  We have synthesized two novel phthalocyanines, (m-SF5PhO)(8)PcCu (7b) and (p-SF5PhO)(8)PcCu (7c), in order to investigate their flying-seed-like mesomorphism. Their phase transition behavior and the mesophase structure have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. Very interestingly, the derivative (m-SF5PhO)(8)PcCu (7b) substituted a SF 5 group at m-position showed a Col(10)(P2(1)/a) (= p2gg) mesophase from rt to 315.0 degrees C, whereas the derivative (p-SF5PhO)(8)PcCu (7c) substituted a SF 5 group at p-position showed a crystalline (K) phase from rt to the decomposition temperature at ca. 336 degrees C without showing mesomorphism. Thus, the novel phthalocyanine derivative (m-SF5PhO)(8)PcCu (7b) substituted a strong electron withdrawing SF 5 group at m-position shows only one columnar mesophase in a very wide temperature region from rt to 315.0 degrees C. Furthermore, the Q-band wavelengths (672.2 and 672.1 nm) of the present (m-SF5PhO)(8)PcCu (7b) and (p-SF5PhO)(8)PcCu (7c) are shorter than that (680.3 nm) of the previous PhS (k)} instead of using long alkyl chains, in order to investigate their mesomorphism. Their phase transition behavior and the mesophase structures have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. As the results, [(o-C-1)PhS](8)PcCu (8i), PhS}(8)PcCu (8k) show a Col tet. o mesophase at 314.9 similar to 362.9 degrees C, a Col(ro) (P2m) mesophase at 287.4 similar to 334.2 degrees C and a Col(ro) (P2m) mesophase at 331.8 similar to 386.8 degrees C, respectively. Very interestingly, each of the derivatives thus exhibits a columnar mesophase at very high temperatures. The mesomorphism is apparently originated from the novel bulky groups (i similar to k). It is also noteworthy that the Q-bands of the present PhScontaining Pc derivatives 8i similar to 8k in THF significantly red-shift by about 35 nm in comparison with those of the corresponding PhO-containing derivatives in THF.
  WORLD SCI PUBL CO INC, English, Scientific journal
  DOI：https://doi.org/10.1142/S1088424615500479
  DOI ID：10.1142/S1088424615500479, ISSN：1088-4246, eISSN：1099-1409, Web of Science ID：WOS:000355750500001
• Flying-seed-like liquid crystals. Part 4:dagger a novel series of bulky substituents inducing mesomorphism instead of using long alkyl chains　　　　　　　　　　　　　　　
  Miho Yoshioka; Kazuchika Ohta; Mikio Yasutake
  RSC ADVANCES, Volume：5, Number：18, First page：13828, Last page：13839, 2015, [Reviewed]
  We synthesized a novel series of flying-seed-like derivatives (3a-g) based on phthalocyaninato copper(II) (abbreviated as PcCu) substituted by bulky groups {PhO (a), (o-C-1)PhO (b), (m-C-1)PhO (c), (p-C-1)PhO (d), [m, p-(C-1)(2)]PhO (e), [m, m'-(C-1)(2)]PhO (f), and [m,p,m'-(C-1)(3)]PhO (g)} instead of using long alkyl chains, in order to investigate their mesomorphism. Their phase transition behaviour and the mesophase structures were established using a polarizing optical microscope, a differential scanning calorimeter, a thermogravimetry analyser and a temperature-dependent small angle X-ray diffractometer. It was demonstrated that (PhO)(8)PcCu (3a) and [(p-C-1)PhO](8)PcCu (3d) show no mesophase, whereas PhO}(8)PcCu (3e), {[m,m'-(C-1)(2)]PhO}(8)PcCu (3f), and {[m, p, m'-(C-1)(3)] PhO}(8)PcCu (3g) show various kinds of columnar mesophases of Col(ro)(P2(1)/a), Col(ro)(P2(1)/a), Col(ro)(C2/m) and Col(tet.o), respectively, while (1,3,5)cyclophanes　　　　　　　　　　　　　　　
  M Yasutake; K Araki; M Zhou; R Nogita; T Shinmyozu
  EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Number：7, First page：1343, Last page：1351, Apr. 2003, [Reviewed]
  5,7,9-Trimethyl[33](1,3,5)cyclophane (1), with two binding sites of different donating ability, adopts a C-3 conformation both in the solid state (-170 degreesC) and in CD2Cl2 solution at -90 degreesC. 5,7,9-Trimethyl[3(3)](1,3,5)cyclophane-2,11,20-trione (9) has the same C-3 symmetry, while [3(3)](1,3,5)cyclophane-2,11,20-trione (12) adopts the C-3 structure in the solid state (-170 degreesC). The structures of I and 9 are the first examples Of C-3 or C-3h symmetries in the [3(3)](1,3,5)cyclophanes; their preferred conformers are C-s both in solution and in the solid state. The cyclophane I shows much stronger donating ability than the parent [3(3)](1,3,5)cyclophane (2). In the TCNQ-F-4 (1:1) complex of 1, the donor (D) and the acceptor (A) are stacked alternately, with partial and complete D-A overlaps being observed in the solid state (-170 degreesC) in the forms of partial D-A overlap of the methyl-substituted benzene face and TCNQ-F-4 and of nearly complete D-A overlap of the methyl-unsubstituted benzene face and TCNQ-F-4. The former type of overlap is generally observed in the TCNQ-F-4 complexes of the [3(n)]cyclophanes, and the transannular D-A distance (3.22 Angstrom) is much shorter than that in the latter (3.58 Angstrom). This supports the idea that the methyl-substituted benzene ring interacts more strongly than the methyl-unsubstituted benzene ring with the acceptor. Consistently with this, two types of acceptor columns are observed, and the transannular distances between acceptors are 3.45 Angstrom for the methyl-unsubstituted side and 3.26 Angstrom for the methyl-substituted side. In the 2,11,20-trithia[3(3)](1,3,5)cyclophane (4)-TCNQ-F-4 (1:1) complex, an alternating D-A stacking similar to that in [33](1,3,5)cyclophane (2)-TCNQ-F-4 (1:1) is observed. The acceptors are stacked in a parallel fashion and form an infinite column, the A-A distance in the (4)-TCNQ-F-4 (1:1) complex being 3.10 Angstrom, and the acceptors in the unit cell are arranged parallel in a plane, the A-A distance being 3.12 Angstrom.
  WILEY-V C H VERLAG GMBH, English, Scientific journal
  ISSN：1434-193X, Web of Science ID：WOS:000182125100023
• Crystal structure of methyl endo-8-cyano-exo-8-methyl-3-oxo-2-oxabicyclo[2.2.2]oct-5-ene-6-carboxylate　　　　　　　　　　　　　　　
  T Shimo; M Yasutake; T Shinmyozu; K Somekawa
  ANALYTICAL SCIENCES, Volume：19, Number：3, First page：471, Last page：472, Mar. 2003, [Reviewed]
  A photochemical cycloaddition reaction of methyl 2-pyrone-5-carboxylate with methacrylonitrile mainly gave a [4 + 2] cycloadduct, assigned as methyl endo-8-cyano-exo-8-methyl-3-oxo-2-oxabicyclo[2.2.2]oct-5-ene-6-carboxylate, whose structure was determined by an X-ray diffraction study. The formation of the cycloadduct was reasonably explained by considering a biradical intermediate having a less steric hindrance between the methoxycarbonyl group and the cyano group.
  JAPAN SOC ANALYTICAL CHEMISTRY, English, Scientific journal
  ISSN：0910-6340, Web of Science ID：WOS:000181557800029
• Structurally isomeric two pyridino macrocycles: Complexation and structures　　　　　　　　　　　　　　　
  Hiroyuki Takemura; Noriyoshi Kon; Mikio Yasutake; Teruo Shinmyozu
  Tetrahedron, Volume：59, Number：3, First page：427, Last page：431, Jan. 2003, [Reviewed]
  Pyridine-based, structurally isomeric two macrocyclic compounds displayed a remarkably different complexation nature. The cage-type compound has an ideal structure for spherical cations, especially for the NH4+ ion, but the reaction with some transition metals and Ln3+ produced its protonated species. On the other hand, its isomer formed complexes with alkali metals and lanthanides (1:1) and also with transition metals. Some structures of the complexes were clarified by crystallographic analyses. © 2003 Elsevier Science Ltd. All rights reserved.
  English, Scientific journal
  DOI：https://doi.org/10.1016/S0040-4020(02)01457-6
  DOI ID：10.1016/S0040-4020(02)01457-6, ISSN：0040-4020, SCOPUS ID：0037434003
• An alternative synthetic route of [35](1,2,3,4,5)cyclophane, and structural properties of multibridged [3n]cyclophanes and their charge-transfer complexes in the solid state　　　　　　　　　　　　　　　
  Mikio Yasutake; Toru Koga; Youichi Sakamoto; Shingo Komatsu; Ming Zhou; Katsuya Sako; Hitoshi Tatemitsu; Satoru Onaka; Yoshio Aso; Shinobu Inoue; Teruo Shinmyozu
  Journal of the American Chemical Society, Volume：124, Number：34, First page：10136, Last page：10145, Aug. 2002, [Reviewed]
  To develop an improved synthetic route to [36](1,2,3,4,5,6)cyclophane (CP) 2, a more practical synthetic route to [35](1,2,3,4,5)CP 3 than the original one was developed, which started from [32](1,3)CP 7 via [34](1,2,4,5)CP 5. The fundamental structural parameters of [3n]CPs (n = 3-6) in the solid state were elucidated, and the observed structures were in good agreement with the most stable conformers in solution and those predicted by the theoretical calculations. In the case of [36]CP 2, the most stable C6h structure was observed in the crystal structure of the 2-TCNQ-F4 (1:1) complex, whereas the highly strained structure with a D6h symmetry was observed in the crystal structure of 2 and the 2:TCNQ:benzene (1:1:1) complex because of a severe disorder problem. [3n]CPs (n >
  3) showed reversible redox processes, and 2 (+0.39 V vs Fc/Fc+, Cl2CHCHCl2) showed the lowest first half-wave oxidation potential [E1/2 (I)] in [3n]CPs. The E1/2 (I) data support the strong donating ability of 2 and its lower homologues. This is attributed to their molecular structures where effective hyperconjugation between the benzyl hydrogens and benzene ring is possible. By taking advantage of the strong electron-donating ability of [3n]CPs, their CT complexes with TCNE, TCNQ, and TCNQ-F4were prepared, and their crystal structural properties were examined. The single-crystal conductivity data of the CT complexes indicated that the TCNQ-F4 complexes showed higher conductivities than the corresponding TCNQ complexes mainly due to a larger charge separation. Among the [3n]CP-TCNQ complexes, the [33](1,3,5)CP 6-TCNQ-F4 (1:1) complex showed the highest conductivity (10-4 S cm-1), and this was ascribed to the formation of an infinite column of partially overlapped acceptors with a short acceptor-acceptor distance, while the formation of such a column was not observed in the 2-TCNQ-F4 complex. Although the conductivities of the cyclophane-CT complexes are much lower than those of the TTF related complexes, this study successfully provides the basic knowledge for understanding the CT interactions in the solid state.
  English, Scientific journal
  DOI：https://doi.org/10.1021/ja012363k
  DOI ID：10.1021/ja012363k, ISSN：0002-7863, PubMed ID：12188678, SCOPUS ID：0037190056
• Crystal structure of 1 : 1 complex crystal between 4-(3-methoxybenzyloxy)6-methyl-2-pyrone and maleimide　　　　　　　　　　　　　　　
  T Shimo; H Yano; M Yasutake; T Shinmyozu; K Somekawa
  ANALYTICAL SCIENCES, Volume：18, Number：8, First page：965, Last page：966, Aug. 2002, [Reviewed]
  JAPAN SOC ANALYTICAL CHEMISTRY, English, Scientific journal
  ISSN：0910-6340, Web of Science ID：WOS:000177500200024
• Crystal structures of 4-methoxy-6-methyl- and 4-hydroxy-6-methyl-2-pyrones　　　　　　　　　　　　　　　
  T Shimo; M Yasutake; T Shinmyozu; K Somekawa
  ANALYTICAL SCIENCES, Volume：18, Number：5, First page：613, Last page：614, May 2002, [Reviewed]
  JAPAN SOC ANALYTICAL CHEMISTRY, English, Scientific journal
  ISSN：0910-6340, Web of Science ID：WOS:000175643000022
• A study of C-F center dot center dot M+ interaction: Metal complexes of fluorine-containing cage compounds　　　　　　　　　　　　　　　
  H Takemura; S Nakashima; N Kon; M Yasutake; T Shinmyozu; T Inazu
  JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Volume：123, Number：38, First page：9293, Last page：9298, Sep. 2001
  The C-F . . .M+ interaction was investigated by observation of the NMR spectroscopic changes and complexation studies between metal cations and the cage compounds 1 and 2 which have fluorobenzene units as donor atoms. As a result, the interaction was detected with. all of the metal cations which form. complexes with 1 and 2. The stability of the complexes of I and 2 was determined by the properties of the metal cations (ionic radii and degree of hydrolysis), not by the hard-soft nature of the cations. Crystallographic analyses of Tl+ subset of 1 and La3+ subset of 2 provided structural information (interatomic distances and bond angles), and the bond strengths, C-F . . .M+, O . . .M+, and N . . .M+, were estimated by Brown's equation based on the structural data. Short C-F . . . Tl+ (2.952-3.048 Angstrom) distances were observed in the complex Tl+ subset of 1. The C-F bond lengths in the complexes, Tl+ subset of 1 and La3+ subset of 2, are elongated compared to those of the metal-free compounds. Interestingly, no solvent molecules including water molecules were coordinated to La3+ in the La3+ subset of 2. The stabilization energy of cation-dipole interaction was calculated on the basis of the data from X-ray crystallographic analysis, and it is roughly consistent with the -DeltaH values estimated in solution. Thus, the C-F . . .M+ interaction can be expressed by the cation-dipole interaction. This result explains the fact that compound I which has fluorine atom as hard donor strongly binds soft metals such as Ag+ and Tl+. Furthermore, it was concluded that the fluorobenzene unit has a poor electron-donating ability compared to that of ether oxygen or amine nitrogen, and thus the ratio of the coordination bond in C-F . . .M+ is small. The specific and remarkable changes in the H-1, C-13, and F-19 NMR spectra were observed accompanied by the complexation between M+ and the hosts 1 and 2. These spectral features are important tools for the investigation of the C-F . . .M+ interaction. Furthermore, F . . . Tl+ spin couplings were observed at room temperature in the Tl+ subset of 1, 2 (J(F-Tl) = 2914 Hz for Tl+ subset of 1 and 4558 Hz for Tl+ subset of 2), and these are clear and definitive evidence of the interaction.
  AMER CHEMICAL SOC, English, Scientific journal
  ISSN：0002-7863, Web of Science ID：WOS:000171169700011
• Alternative general synthetic routes to [2.2]cyclophanes and [3,2]cyclophanes from [3.3]cyclophane-2,11-diones by photodecarbonylation, and a structural study of [3.2]metacyclophanes　　　　　　　　　　　　　　　
  H Isaji; M Yasutake; H Takemura; K Sako; H Tatemitsu; T Inazu; T Shinmyozu
  EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Number：13, First page：2487, Last page：2499, Jul. 2001, [Reviewed]
  Photodecarbonylation of [3.3]cyclophane-2,11-diones, which are readily prepared by TosMIC coupling, affords [2.2]cyclophanes in high yield. This method also provides a general synthetic method for [3.2]cyclophan-2-ones by taking advantage of the fact that this photochemical reaction proceeds in a stepwise manner through [3.2]cyclophan-2-ones. A series of [2.2]cyclophanes, [3.2]cyclophanes, and [3.3]cyclophanes can thus be made available from the common precursor [3.3]cyclophane-2,11-diones. In sharp contrast to the preferred syn geometry of [3.3]metacyclophanes, [3.2]metacyclophanes adopt anti geometries and the aryl ring inversion process is observed by variable-temperature H-1 NMR spectroscopy. In the crystalline state, the two aryl rings of anti-[3.2]metacyclophanes are almost parallel in spite of the unsymmetrical bridge length; they overlap only at the C-9 and C-17 positions, and the transannular distances are shorter than the corresponding distances in [3.3]metacyclophane-2,11-dione.
  WILEY-V C H VERLAG GMBH, English, Scientific journal
  ISSN：1434-193X, Web of Science ID：WOS:000169648100009
• Synthesis, Electronic Spectra, and Crystal Structural Properties of Fluorinated [33](1,3,5)cyclophanes　　　　　　　　　　　　　　　
  Toru Koga; Mikio Yasutake; Teruo Shinmyozu
  Organic Letters, Volume：3, Number：10, First page：1419, Last page：1422, May 2001, [Reviewed]
  matrix presented Trifluoro- and hexafluoro[33](1,3,5)cyclophanes 3 and 4 were synthesized with TosMIC coupling as a key reaction. The π-π* absorption bands show blue shifts as the number of fluorine atoms is increased. In the crystalline state, characteristic stacking with the fluorinated benzene rings facing each other is observed in both cases.
  English, Scientific journal
  DOI：https://doi.org/10.1021/ol010003w
  DOI ID：10.1021/ol010003w, ISSN：1523-7060, SCOPUS ID：0001071763
• A study of C-F center dot center dot center dot M+ interaction: Alkali metal complexes of the fluorine-containing cage compound　　　　　　　　　　　　　　　
  H Takemura; N Kon; M Kotoku; S Nakashima; K Otsuka; M Yasutake; T Shinmyozu; T Inazu
  JOURNAL OF ORGANIC CHEMISTRY, Volume：66, Number：8, First page：2778, Last page：2783, Apr. 2001
  The C-F . . .M+ interaction was investigated by employing a cage compound 1 that has four fluorobenzene units. The NMR (H-1, C-13, and F-19) spectra and X-ray crystallographic analyses of 1 and its metal complexes showed clear evidence of the interaction. Short C-F Mt distances (C-F . . .K+, 2.755 and 2.727 Angstrom; C-F . . . Cs+, 2.944 and 2.954 Angstrom) were observed in the crystalline state of K+ subset of 1 and Cs+ subset of 1. Furthermore, the C-F bond lengths were elongated by the interaction with the metal cations. By calculating Brown's bond valence, it is shown that the contribution of the C-F unit to cation binding is comparable or greater than the ether oxygen in the crystalline state. Representative spectroscopic changes implying the C-F . . .M+ interaction were observed in the NMR (H-1, C-13,and F-19) spectra. In particular, Cs-133-F-19 spin coupling (J = 54.9 Hz) was observed in the Cs+ complex.
  AMER CHEMICAL SOC, English, Scientific journal
  ISSN：0022-3263, Web of Science ID：WOS:000168258600033
• Formation and structural features of novel cage compounds with a pentacyclo[6.4.0.0(3,7).0(4,11).0(5,10)]dodecane skeleton via photolysis of [3(3)](1,3,5)cyclophane　　　　　　　　　　　　　　　
  K Matohara; C Lim; M Yasutake; R Nogita; T Koga; Y Sakamoto; T Shinmyozu
  TETRAHEDRON LETTERS, Volume：41, Number：35, First page：6803, Last page：6807, Aug. 2000, [Reviewed]
  The photolysis of [3(3)](1,3,5)cyclophane 8 in MeOH:2N HCl (17:1 v/v) afforded new polycyclic caged dimethoxy and methoxy-hydroxy compounds 12 and 13 with a novel pentacyclo[6.4.0.0(3,7).0(4,11).0(5,10)]- dodecane skeleton 7, in addition to methyl ether 9c with the previously reported skeleton 6. The unique structural features of 12 and 13 were elucidated by X-ray structural analysis. (C) 2000 Elsevier Science Ltd. All rights reserved.
  PERGAMON-ELSEVIER SCIENCE LTD, English, Scientific journal
  ISSN：0040-4039, Web of Science ID：WOS:000089031200024
• Inner C-arylation of a doubly N-confused porphyrin–Pd complex in toluene—the possibility of a Pd3+ intermediate
  Hiroyuki Furuta; Hiromitsu Maeda; Atsuhiro Osuka; Mikio Yasutake; Teruo Shinmyozu; Yuichi Ishikawa
  Chemical Communications, Number：13, First page：1143, Last page：1144, 2000
  Royal Society of Chemistry (RSC), Scientific journal
  DOI：https://doi.org/10.1039/b003022h
  DOI ID：10.1039/b003022h, ISSN：1359-7345, eISSN：1364-548X
• Formation of a novel cage compound with a Pentacyclo[6.3.0.1(4,11).0(2,6).0(5,10)]dodecane skeleton by photolysis of [3(4)](1,2,4,5)cyclophane　　　　　　　　　　　　　　　
  C Lim; M Yasutake; T Shinmyozu
  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Volume：39, Number：3, First page：578, Last page：+, 2000, [Reviewed]
  WILEY-V C H VERLAG GMBH, English, Scientific journal
  ISSN：1433-7851, Web of Science ID：WOS:000085230900032
• Photolysis of [3(4)](1,2,3,5)cyclophane: formation of a pentacyclo[6.3.1.1(6,10).0(3,7).0(4,10)]dodecane skeleton with abnormally elongated C-C single bonds　　　　　　　　　　　　　　　
  C Lim; M Yasutake; T Shinmyozu
  TETRAHEDRON LETTERS, Volume：40, Number：37, First page：6781, Last page：6784, Sep. 1999, [Reviewed]
  The photolysis of [3(4)](1,2,3,5)cyclophane 5 in H2O-saturated CH2Cl2 produced the novel polycyclic caged diol 6 with a pentacyclo[6.3.1.1(6,10).0(3,7).0(4,10)]dodecane skeleton 4, which has abnormally elongated C-C single bonds (1.624 Angstrom). The structural features of 6 were studied using the X-ray structural analysis and ab initio MO calculations. (C) 1999 Elsevier Science Ltd. All rights reserved.
  PERGAMON-ELSEVIER SCIENCE LTD, English, Scientific journal
  ISSN：0040-4039, Web of Science ID：WOS:000082199900021
• Multibridged [3(n)]cyclophanes, 7 Improved synthesis, structure, and cycloaddition reaction of [3(4)](1,2,4,5)cyclophane　　　　　　　　　　　　　　　
  W Sentou; T Satou; M Yasutake; C Lim; Y Sakamoto; T Itoh; T Shinmyozu
  EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Number：5, First page：1223, Last page：1231, May 1999, [Reviewed]
  The modified synthetic route to [3(4)](1,2,4,5)cyclophane (3) provides gram quantities of this compound in fewer steps than the conventional routes. The cycloaddition of 3 with dicyanoacetylene (12) gave barrelenophane 13, which transformed into semibullvalenophane 15 on photoirradiation. This transformation (13 --> 15) is in sharp contrast to the case of Boekelheide's [2(4)]barrelenophane, where cyclooctatetraenophane is obtained. The X-ray structural was analyses of 3, 13, and 15 demonstrates their unique structures.
  WILEY-V C H VERLAG GMBH, English, Scientific journal
  ISSN：1434-193X, Web of Science ID：WOS:000080228100030
• Synthesis of a new pyridinophane macrocycle with carbamate functionality via novel CO2 insertion reaction　　　　　　　　　　　　　　　
  D Noda; M Yasutake; H Takemura; T Shinmyozu
  TETRAHEDRON LETTERS, Volume：40, Number：17, First page：3447, Last page：3450, Apr. 1999, [Reviewed]
  The coupling reaction of 2, 11-diaza[3.3](2,6)pyridinophane 3 and N-tosyl-diethanolamine ditosylate 4 in the presence of M2CO3 (M = Cs+, K+) in DMF afforded a novel macrocycle 2 with a carbamate moiety, whose structure was confirmed by an X-ray structural analysis, (C) 1999 Elsevier Science Ltd. All rights reserved.
  PERGAMON-ELSEVIER SCIENCE LTD, English, Scientific journal
  ISSN：0040-4039, Web of Science ID：WOS:000079737000043

• PB18 Synthesis and Characterization of Discotic Liquid-Crystalline Compounds Having Trialkylsilyl Groups　　　　　　　　　　　　　　　
  Miyazaki Yutaro; Yasutake Mikio; Hirose Takuji
  Number：2012, First page："PB18, Last page：1"-"PB18-2", 20 Aug. 2012
  Novel discotic liquid-crystalline materials were synthesized from triphenylene and hexabenzocoronene by attaching trialkylsilyl groups in the side chains. These compounds dissolved well in hexane, toluene, chloroform, diethyl ether and THF. DSC, POM and XRD measurements proved that triphenylene and hexabenzocoronene derivatives exhibit Col r and Col ho masophases respectively, over wide temperature ranges. Trialkylsilyl group was shown to be an effective flexible moiety of liquid-crystalline materials to improve solubility in organic solvents.
  Japanese Liquid Crystal Society, Japanese
  CiNii Articles ID：110009668916, CiNii Books ID：AA11639022
• PA19 Synthesis and characterization of a pyrene derivative having thiophene moieties　　　　　　　　　　　　　　　
  Watabe Mizuki; Takai Hiroaki; Yasutake Mikio; Hirose Takuji
  Number：2012, First page："PA19, Last page：1"-"PA19-2", 20 Aug. 2012
  In order to develop columnar discotic liquid-crystalline compounds with high charge transport ability, a pyrene derivative having a thiophene moiety in the side chains was synthesized and the physical and thermal properties were studied by POM, DSC, and XRD measurements. It was shown that an ordered hexagonal columnar (Col_) phase appears in the temperature range of more than 130 degrees showing the liquid crystalline phase is stable. The hole mobility determined by the time-of-flight (TOF) method was 4.8×10^<-3>cm^2V^<-1>s^<-1> in the Col_ phase at 140℃.
  Japanese Liquid Crystal Society, Japanese
  CiNii Articles ID：110009668866, CiNii Books ID：AA11639022
• Solvent control of optical resolution of 2-amino-1-phenylethanol using dehydroabietic acid　　　　　　　　　　　　　　　
  Kayoko Taniguchi; Marie Aruga; Mikio Yasutake; Takuji Hirose
  ORGANIC & BIOMOLECULAR CHEMISTRY, Volume：6, Number：3, First page：458, Last page：463, Feb. 2008
  The optical resolution of 2-amino-1-phenylethanol (2-APE) by the solvent switch method was investigated using dehydroabietic acid (DAA), a natural chiral acid obtained as one of the main components of disproportionated rosin. The solvent dependency of optical rotation measurements of 2-APE, DAA and the diastereomeric salts suggested solvent control of optical resolution. Both (R)- and (S)-2-APE were resolved, as the first success for aminoalcohols, only by changing the resolving solvents: (S)-2-APE was obtained in high optical purity by a single crystallization operation with polar solvents (epsilon > 50), whereas the efficiency was lower for (R)-2-APE using less polar solvents (20 < epsilon < 40). The results were compared and discussed with reference to the crystal structures of the diastereomeric salts.
  ROYAL SOC CHEMISTRY, English
  DOI：https://doi.org/10.1039/b717071h
  DOI ID：10.1039/b717071h, ISSN：1477-0520, CiNii Articles ID：80019393378, PubMed ID：18219414, Web of Science ID：WOS:000253423400010
• ピレン骨格を有する伝導性ディスコチック液晶化合物の合成　　　　　　　　　　　　　　　
  安武幹雄
  Volume：第6号(平成19年度), 2008
• Crystal Structures of (S)- and (R)-1-Amino-2-propanol/Dehydroabietic Acid Salts　　　　　　　　　　　　　　　
  Hirose, T; Odagiri, E; Taniguchi, K; Yasutake, M
  Volume：24, First page：X9, Last page：X10, 2008
  DOI：https://doi.org/10.2116/analscix.24.x9
  DOI ID：10.2116/analscix.24.x9, ISSN：1348-2238, CiNii Articles ID：80019432432
• ピレン骨格を有する伝導性ディスコチック液晶化合物の合成　　　　　　　　　　　　　　　
  安武幹雄
  総合研究機構研究プロジェクト研究成果報告書, Volume：第6号(平成19年度), 2008
• Crystal Structures of (S)- and (R)-1-Amino-2-propanol/Dehydroabietic Acid Salts　　　　　　　　　　　　　　　
  Hirose, T; Odagiri, E; Taniguchi, K; Yasutake, M
  Anal. Sci., Volume：24, First page：X9, Last page：X10, 2008
  DOI：https://doi.org/10.2116/analscix.24.x9
  DOI ID：10.2116/analscix.24.x9, ISSN：1348-2238, CiNii Articles ID：80019432432
• Synthesis and phase structures of novel pi-acceptor discotic liquid crystalline compounds having a pyrenedione core　　　　　　　　　　　　　　　
  Mikio Yasutake; Takashi Fujihara; Akira Nagasawa; Keiichi Moriya; Takuji Hirose
  European Journal of Organic Chemistry, Volume：2008, Number：24, First page：4120, Last page：4125, 2008
  DOI：https://doi.org/10.1002/ejoc.200800360
  DOI ID：10.1002/ejoc.200800360, ISSN：1434-193X, CiNii Articles ID：80019737426
• Resolution of alpha-methylbenzylamine via diastereomeric salt formation using the naturally based reagent N-tosyl-(S)-phenylalanine together with a solvent switch technique　　　　　　　　　　　　　　　
  Takuji Hirose; Muksana Begum; Md Sadequl Islam; Kayoko Taniguchi; Mikio Yasutake
  Tetrahedron-Asymmetry, Volume：19, Number：14, First page：1641, Last page：1646, 2008
  DOI：https://doi.org/10.1016/j.tetasy.2008.06.035
  DOI ID：10.1016/j.tetasy.2008.06.035, ISSN：0957-4166, CiNii Articles ID：80019725383
• Synthesis of novel chiral 1,3-aminophenols and application for the enantioselective addition of diethylzinc to aldehydes　　　　　　　　　　　　　　　
  Xiao-Feng Yang; Zhao-Hui Wang; Tomoaki Koshizawa; Mikio Yasutake; Guang-You Zhang; Takuji Hirose
  TETRAHEDRON-ASYMMETRY, Volume：18, Number：10, First page：1257, Last page：1263, Jun. 2007
  Novel chiral 1,3-aminophenols were efficiently synthesized by applying a Friedel-Crafts reaction and optical resolution. The catalytic activity of the aminophenols was studied for the addition of diethylzinc to benzaldehyde. The results showed that (S)-5a with bulky tert-butyl groups on the stereogenic carbon atom and 4,6-positions of phenol favored higher enantio selectivity (94% ee). The same ligand was also used with other aldehydes, to give optically active alcohols in good chemical yields and cc values (up to 99%). (C) 2007 Elsevier Ltd. All rights reserved.
  PERGAMON-ELSEVIER SCIENCE LTD, English
  DOI：https://doi.org/10.1016/j.tetasy.2007.05.027
  DOI ID：10.1016/j.tetasy.2007.05.027, ISSN：0957-4166, CiNii Articles ID：80018352678, Web of Science ID：WOS:000248103800018
• Dehydroabietic acid esters as chiral dopants for nematic liquid crystals　　　　　　　　　　　　　　　
  Hiroaki Shitara; Marie Aruga; Erni Odagiri; Kayoko Taniguchi; Mikio Yasutake; Takuji Hirose
  BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, Volume：80, Number：3, First page：589, Last page：593, Mar. 2007
  Dehydroabietic acid esters were prepared as new chiral dopants for the nematic liquid crystals. The magnitude of the helical twisting power (HTP) was good due to simple but rigid three-ring structure and two axial methyl groups. The relationship between the HTP or MHTP (molar helical twisting power) values and the terminal structures was studied. Considering the synthetic accessibility and their miscibility with liquid crystals, the acid was shown to be a good candidate as the scaffold of chiral dopants for the nematic liquid crystals.
  CHEMICAL SOC JAPAN, English
  DOI：https://doi.org/10.1246/bcsj.80.589
  DOI ID：10.1246/bcsj.80.589, ISSN：0009-2673, eISSN：1348-0634, CiNii Articles ID：10018877486, Web of Science ID：WOS:000245885000025
• Gas-phase-assisted surface polymerization of methyl methacrylate with Fe(0)/TsCl initiator system　　　　　　　　　　　　　　　
  Yoshito Andou; Mikio Yasutake; Jae-Mun Jeong; Masao Kaneko; Haruo Nishida; Takeshi Endo
  JOURNAL OF APPLIED POLYMER SCIENCE, Volume：103, Number：3, First page：1879, Last page：1886, Feb. 2007
  To obtain a high polymer coated Fe(0) surface, gas-phase-assisted surface polymerization (GASP) of methyl methacrylate (MMA) was investigated using a zero-valent iron (Fe(0))/p-toluene sulfonylchloride (TsCl) initiator system, resulting in successful high polymer production on the solid surface. GASP was found to be initiated by radical species that might have been generated via redox reactions with Fe(0), Fe(II), Fe(III), and TsCl. From H-1-NMR analysis, the p-toluene sulfonyl group was found at one end of the polymer chain. The molecular weight of obtained PMMA drastically decreased with increase in the composition ratio of Fe(0) in the initiator system, and increased with increase in polymer yield. From the results, it was assumed that the physically controlled polymerization of MMA proceeded by immobilized active species at gas-solid interfaces. (c) 2006 Wiley Periodicals, Inc.
  WILEY-BLACKWELL, English
  DOI：https://doi.org/10.1002/app.25270
  DOI ID：10.1002/app.25270, ISSN：0021-8995, eISSN：1097-4628, CiNii Articles ID：80017903740, Web of Science ID：WOS:000243013800062
• ＰＥＴ（Ｐｒｏｔｏｎ Ｅｌｅｃｔｒｏｎ Ｔｒaｎｓｆａｒ）が可能な液晶性化合物及び分子デバイスの合成と挙動　　　　　　　　　　　　　　　
  安武幹雄
  Volume：第5号(18年度), First page：549, Last page：550, 2007
• Designed surface modification by photo-induced vapor phase assisted surface polymerization of vinyl monomers　　　　　　　　　　　　　　　
  Yoshito Andou; Mikio Yasutake; Haruo Nishida; Takeshi Endo
  JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY, Volume：20, Number：4, First page：523, Last page：528, 2007
  The photo-induced vapor phase assisted surface polymerization (photo-VASP) technique was developed to achieve designed fine 2D and 3D patterns on solid surfaces. When used with pre-patterned photo-masks, photo-VASP, via polymer accumulations, reproduced pre-patterns on glass plate, Si-wafer, and Au-plate surfaces. Patterns from covalently bonded polymer were achieved with immobilized photo initiators. Moreover, a multi-layered 3D pattern was also made of block copolymer chains grafted from the surfaces.
  TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN, English
  DOI：https://doi.org/10.2494/photopolymer.20.523
  DOI ID：10.2494/photopolymer.20.523, ISSN：0914-9244, CiNii Articles ID：40015602522, Web of Science ID：WOS:000247885900007
• ＰＥＴ（Ｐｒｏｔｏｎ Ｅｌｅｃｔｒｏｎ Ｔｒaｎｓｆａｒ）が可能な液晶性化合物及び分子デバイスの合成と挙動　　　　　　　　　　　　　　　
  安武幹雄
  総合研究機構研究プロジェクト研究成果報告書, Volume：第5号(18年度), First page：549, Last page：550, 2007
• Designed surface modification by photo-induced vapor phase assisted surface polymerization of vinyl monomers　　　　　　　　　　　　　　　
  Yoshito Andou; Mikio Yasutake; Haruo Nishida; Takeshi Endo
  JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY, Volume：20, Number：4, First page：523, Last page：528, 2007
  The photo-induced vapor phase assisted surface polymerization (photo-VASP) technique was developed to achieve designed fine 2D and 3D patterns on solid surfaces. When used with pre-patterned photo-masks, photo-VASP, via polymer accumulations, reproduced pre-patterns on glass plate, Si-wafer, and Au-plate surfaces. Patterns from covalently bonded polymer were achieved with immobilized photo initiators. Moreover, a multi-layered 3D pattern was also made of block copolymer chains grafted from the surfaces.
  TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN, English
  DOI：https://doi.org/10.2494/photopolymer.20.523
  DOI ID：10.2494/photopolymer.20.523, ISSN：0914-9244, CiNii Articles ID：40015602522, Web of Science ID：WOS:000247885900007
• Optical rotation study on solvent dependence of diastereomeric salt discrimination properties　　　　　　　　　　　　　　　
  Kayoko Taniguchi; Rumiko Sakurai; Kenichi Sakai; Mikio Yasutake; Takuji Hirose
  BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, Volume：79, Number：7, First page：1084, Last page：1090, Jul. 2006
  The optical rotation properties have been studied for two diastereomeric salts of four kinds of amine-carboxylic acid salt systems, and the results have been compared among them and their chiral salts. The diastereomeric salts of 2-(4-methylphenyl)-1-phenylethylamine/mandelic acid (1-phenyl-2-(4-methylphenyl)ethylamine; PTE/MA) and alpha-amino-C-caprolactam/N-tosylphenylalanine (ACL/TPA) exhibited relatively large differences in optical rotation values and solvent dependency. In contrast, the diastereomeric salts of alpha-methylbenzylamine/MA and piperazine-2-carboxylic acid t-butylamide/TPA possessed similar optical rotation behavior; the values and solvent dependency were almost identical. These results were discussed in relation to the dielectrically controlled resolution phenomenon for the formers, PTE/MA and ACL/TPA, and were also compared with the crystal structures.
  CHEMICAL SOC JAPAN, English
  DOI：https://doi.org/10.1246/bcsj.79.1084
  DOI ID：10.1246/bcsj.79.1084, ISSN：0009-2673, eISSN：1348-0634, CiNii Articles ID：80019113098, Web of Science ID：WOS:000240078400013
• Synthesis of optically active 4,4,4-trifluoro-3-{4-(4-methoxyphenyl)phenyl}butanoic acid and its application to chiral dopant for nematic liquid crystals　　　　　　　　　　　　　　　
  Kenta Tojo; Yoshio Aoki; Mikio Yasutake; Takuji Hirose
  JOURNAL OF FLUORINE CHEMISTRY, Volume：127, Number：4-5, First page：620, Last page：626, May 2006
  We synthesized an optically active 4,4,4-trifluoro-3-{4-(4-methoxyphenyl)phenyl)butanoic acid (5*). New chiral dopants for nematic liquid crystals were derived from (R)-(-)-5*, and their helical twisting power (HTP) values were measured. Their HTP values were largely influenced by the linkage between the asymmetric frame and the core moiety. The chiral dopant, (R)-(+)-4,4,4-trifluoro-1-(4-hexyloxyphenyl)-3-{4-(4-methoxyphenyl)phenyl}-1-butanone ((R)-(+)-7*) showed the largest HTP value (-21.7 mu m(-1)). (C) 2005 Elsevier B.V. All rights reserved.
  ELSEVIER SCIENCE SA, English
  DOI：https://doi.org/10.1016/j.jfluchem.2005.11.005
  DOI ID：10.1016/j.jfluchem.2005.11.005, ISSN：0022-1139, Web of Science ID：WOS:000237986300024
• 電荷移動能をコアに有する液晶性化合物及び分子デバイスの合成と挙動　　　　　　　　　　　　　　　
  安武幹雄
  Volume：第4号(17年度), 2006
• Crystal structure of (S)-piperazine-2-carboxylic acid t-butylamide/N-Tosyl-(S)-phenylalanine 1:2 salt　　　　　　　　　　　　　　　
  Kayoko Taniguchi; Mikio Yasutake; Takuji Hirose
  Analytical Sciences: X-ray Structure Analysis Online, Volume：22, Number：3, First page：x29, Last page：x30, 2006
  The crystal structure of the title salt was determined by X-ray diffraction. The compound crystallizes in a monoclinic space group, C2, with cell parameters a = 43.023(3)Å, b = 5.8504(5)Å, c = 16.6159(13)Å, β = 93.776(2)°, and Z = 4
  the final residual factor, 0.0678, is for 7078 reflections. 2006 © The Japan Society for Analytical Chemistry.
  Japan Society for Analytical Chemistry, English, Report scientific journal
  DOI：https://doi.org/10.2116/analscix.22.x29
  DOI ID：10.2116/analscix.22.x29, ISSN：1348-2238, CiNii Articles ID：80018193854, SCOPUS ID：70450267741
• 電荷移動能をコアに有する液晶性化合物及び分子デバイスの合成と挙動　　　　　　　　　　　　　　　
  安武幹雄
  総合研究機構研究プロジェクト研究成果報告書, Volume：第4号(17年度), 2006
• Induction and control of columnar mesophase by charge transfer interaction and side chain structures of tetrasubstituted pyrenes　　　　　　　　　　　　　　　
  T Hirose; O Kawakami; M Yasutake
  MOLECULAR CRYSTALS AND LIQUID CRYSTALS, Volume：451, First page：65, Last page：74, 2006
  The induction of the columnar phase is described in which intrinsically crystalline 1,4,6,9-tetraacyloxypyrenes have been mixed with tetranitrofluorenone, TeNF, as an electron acceptor. The pyrene derivative with linear nonyl chains, PC9, has not shown any mesophases using trinitrofluorenone, suggesting that stronger charge transfer interaction is favored by TeNF. The shape of the substituents works to control the mesophase type: the mixture of PC9 and TeNF has formed a rectangular columnar phase, and a hexagonal columnar phase is attained by rounder derivatives bearing branched side chains.
  TAYLOR & FRANCIS LTD, English
  DOI：https://doi.org/10.1080/154214090960081
  DOI ID：10.1080/154214090960081, ISSN：1542-1406, Web of Science ID：WOS:000237383700006
• Cyclophanes within cyclophanes: The synthesis of a pyromellitic diimide-based macrocycle as a structural unit in a molecular tube and its inclusion phenomena　　　　　　　　　　　　　　　
  Tetsuo Iwanaga; Ryoma Nakamoto; Mikio Yasutake; Hiroyuki Takemura; Katsuya Sako; Teruo Shinmyozu
  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Volume：45, Number：22, First page：3643, Last page：3647, 2006
  WILEY-V C H VERLAG GMBH, English
  DOI：https://doi.org/10.1002/anie.200504499
  DOI ID：10.1002/anie.200504499, ISSN：1433-7851, CiNii Articles ID：80019070751, Web of Science ID：WOS:000238068000015
• Crystal Structure of (S)-Piperazine-2-carboxylic acid t-butylamide/N-Tosyl-(S)-phenylalanine 1:2 Salt　　　　　　　　　　　　　　　
  K. Taniguchi; M. Yasutake; T. Hirose
  Anal. Sci., Volume：22, First page：X29, Last page：X30, 2006
  DOI：https://doi.org/10.2116/analscix.22.x29
  DOI ID：10.2116/analscix.22.x29, ISSN：1348-2238, CiNii Articles ID：80018193854
• Gas-phase assisted surface polymerization of vinyl monomers with Fe-based initiating systems　　　　　　　　　　　　　　　
  Y Andou; M Yasutake; JM Jeong; H Nishida; T Endo
  MACROMOLECULAR CHEMISTRY AND PHYSICS, Volume：206, Number：17, First page：1778, Last page：1783, Sep. 2005
  Gas-phase assisted surface polymerization (GASP) of methyl methacrylate (MMA) and styrene (St) was investigated with Fe-based radical initiating systems, FeCl2/ 2,2'-bipyridine (Bpy)/methyl alpha-bromophenylacetate (MBPA), etc. GASP with these initiating systems proceeded to produce corresponding polymers on substrate surfaces. The resulting PMMA had very high PDI values, suggesting an uncontrolled reaction. In an attempt to control the GASP, polymerization with a simple initiating system, Fe(0)/MBPA, was examined on Fe(0)-metal surfaces, resulting in significant polymerization activity to produce high-molecular-weight PMMA. The results of time-course tests on GASP of MMA and St suggested that a change had taken place to produce physically controlled propagation sites on the Fe(0) powder surfaces.
  WILEY-V C H VERLAG GMBH, English
  DOI：https://doi.org/10.1002/macp.200500151
  DOI ID：10.1002/macp.200500151, ISSN：1022-1352, CiNii Articles ID：80017577685, Web of Science ID：WOS:000231996600009
• Synthesis and characterization of novel Cu(II)-bipyridine complexes having functional groups and their application toward molecular recognition　　　　　　　　　　　　　　　
  T Kojima; H Kitaguchi; Y Tachi; M Yasutake; Y Naruta; Y Matsuda
  INORGANICA CHIMICA ACTA, Volume：358, Number：13, First page：3592, Last page：3600, Sep. 2005
  Two kinds of Cu(II) complexes having 2,2'-bipyridine derivatives with two 1-naphthoylamide groups or two ethyl dimethylmalonylamide moieties at 6 and 6' positions as ligands were prepared and characterized by X-ray crystallography and spectroscopic methods. Those ligands bound to the Cu(II) centers in a tetradentate fashion including two amide oxygen atoms in the equatorial planes. Those complexes were found to recognize carboxylic acids as guest molecules by coordination and additional non-covalent interactions, including intramolecular pi-pi interactions or hydrogen bonding. (c) 2005 Elsevier B.V. All rights reserved.
  ELSEVIER SCIENCE SA, English
  DOI：https://doi.org/10.1016/j.ica.2005.06.007
  DOI ID：10.1016/j.ica.2005.06.007, ISSN：0020-1693, CiNii Articles ID：80017575426, Web of Science ID：WOS:000232384400006
• Crystal structure of 3,4-dihydro-2H-1,5-benzodioxepine-7,8-dicarboxylic acid　　　　　　　　　　　　　　　
  Mikio Yasutake; Seitaro Yamaguchi; Takuji Hirose
  Analytical Sciences: X-ray Structure Analysis Online, Volume：21, Number：5, First page：x81, Last page：x82, 2005
  The crystal structure of the title compound, having a 6 - 7 membered ring, was determined by the X-ray diffraction method. The compound crystallized in the monoclinic space group C2/c with cell parameters a = 4.2679(14)Å, b = 21.128(6)Å, c = 11.372(4)Å, β = 95.354(10), and Z = 4
  the final residual factor was 0.0445 for 1012 reflections. 2005 © The Japan Society for Analytical Chemistry.
  Japan Society for Analytical Chemistry, English, Report scientific journal
  DOI：https://doi.org/10.2116/analscix.21.x81
  DOI ID：10.2116/analscix.21.x81, ISSN：1348-2238, SCOPUS ID：53749103163
• Crystal structure of 3,4-dihydro-2H-1,5-benzodioxepine-7,8-dicarboxylic acid.　　　　　　　　　　　　　　　
  M. Yasutake; S. Yamaguchi; T. Hirose
  X-Ray Structure Analysis Online, Volume：21, First page：X81, Last page：X82, 2005
  DOI：https://doi.org/10.2116/analscix.21.x81
  DOI ID：10.2116/analscix.21.x81, ISSN：1348-2238
• The Ar-Cl center dot center dot center dot HO hydrogen bond of 6-chloro-9-hydroxy-[3.3]metacyclophane　　　　　　　　　　　　　　　
  H Takemura; M Kotoku; M Yasutake; T Shinmyozu
  JOURNAL OF CHEMICAL RESEARCH-S, Volume：12, Number：12, First page：834, Last page：835, Dec. 2004
  The chlorophenol moiety of the titled cyclophane showed intermolecular hydrogen bonds, O-H...OH and C-Cl...HO, in the crystals.
  SCIENCE REVIEWS LTD, English
  ISSN：0308-2342, Web of Science ID：WOS:000227101700017
• The Ar-Cl center dot center dot center dot HO hydrogen bond of 6-chloro-9-hydroxy-[3.3]metacyclophane　　　　　　　　　　　　　　　
  H Takemura; M Kotoku; M Yasutake; T Shinmyozu
  JOURNAL OF CHEMICAL RESEARCH-S, Volume：12, Number：12, First page：834, Last page：835, Dec. 2004
  The chlorophenol moiety of the titled cyclophane showed intermolecular hydrogen bonds, O-H...OH and C-Cl...HO, in the crystals.
  SCIENCE REVIEWS LTD, English
  ISSN：0308-2342, Web of Science ID：WOS:000227101700017
• Photochemical sudy of [3(3)](1,3,5)cyclophane and emission spectral poperties of [3(n)]cyclophanes (n=2-6)　　　　　　　　　　　　　　　
  R Nogita; K Matohara; M Yamaji; T Oda; Y Sakamoto; T Kumagai; C Lim; M Yasutake; T Shimo; CW Jefford; T Shinmyozu
  JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Volume：126, Number：42, First page：13732, Last page：13741, Oct. 2004
  Thephotochemical reaction of [3(3)](1,3,5)cyclophane 2, which is a photoprecursor for the formation of propella[3(3)]prismane 18, was studied using a sterilizing lamp (254 nm). Upon photolysis in dry and wet CH2Cl2 or MeOH in the presence of 2 mol/L aqueous HCl solution, the cyclophane 2 afforded novel cage compounds comprised of new skeletons, tetracyclo[6.3.1.0.O-2,7(4,11)]dodeca-5,9-diene 43, hexacyclo[6.4.0.0.O-2,O-6.O-4,O-11.O-5,10(9,12)]dodecane 44, and pentacyclo[6.4.0.0.O-2,O-6.O-4,11(5,10)]dodecane 45. All of these products were confirmed by the X-ray structural analyses. A possible mechanism for the formation of these photoproducts via the hexaprismane derivative 18 is proposed. The photophysical properties in the excited state of the [3(n)]cyclophanes ([3(n)]CP, n = 2-6) were investigated by measuring the emission spectra and determining the quantum yields and lifetimes of the fluorescence. All [3(n)]CPs show excimeric fluorescence without a monomeric one. The lifetime of the excimer fluorescence becomes gradually longer with the increasing number of the trimethylene bridges. The [3(n)]CPs also shows excimeric phosphorescence spectra without vibrational structures for n = 2, 4, and 5, while phosphorescence is absent for n = 3 and 6. With an increase in symmetry of the benzene skeleton in the [3(3)]- and [3(6)]CPS, the probability of the radiation (phosphorescence) process from the lowest triplet state may drastically decrease.
  AMER CHEMICAL SOC, English
  DOI：https://doi.org/10.1021/ja030032x
  DOI ID：10.1021/ja030032x, ISSN：0002-7863, CiNii Articles ID：80017017541, PubMed ID：15493932, Web of Science ID：WOS:000224685200051
• Physically controlled, free-radical polymerization of vaporized fluoromonomer on solid surfaces　　　　　　　　　　　　　　　
  M Yasutake; Y Andou; S Hiki; H Nishida; T Endo
  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, Volume：42, Number：11, First page：2621, Last page：2630, Jun. 2004
  Gas/vapor-deposition polymerization (GDP) of vinyl monomer is expected to exhibit a unique polyinerization behavior different from its polymerization in the liquid phase. Free-radical GDP of 2,2,3,3,3-pentafluoropropyl methacrylate (FMA) was carried out with a conventional free-radical initiator (azobisisobutyronitrile) on substrate surfaces. A linear relationship between the number-average molecular weight and polymer yield was observed, and the consecutive copolymerization of methyl methacrylate (MMA) and FMA led to the formation of block copolymer P(MMA-block-FMA). These results suggested that the GDP process on substrate surfaces has a living nature. During the process, the active species at growing chain ends may be immobilized on the deposit surface and restricted from the chain-transfer reactions, resulting in a continuation of the propagation reaction. The GDP on substrate surfaces is therefore a physically controlled polymerization process. (C) 2004 Wiley Periodicals, Inc.
  JOHN WILEY & SONS INC, English
  DOI：https://doi.org/10.1002/pola.20129
  DOI ID：10.1002/pola.20129, ISSN：0887-624X, CiNii Articles ID：80016672945, Web of Science ID：WOS:000221527300005
• 9-fluoro-18-hydroxy-[3.3]metacyclophane: Synthesis and estimation of a C-(FH)-H-...-O hydrogen bond　　　　　　　　　　　　　　　
  H Takemura; M Kotoku; M Yasutake; T Shinmyozu
  EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Number：9, First page：2019, Last page：2024, Apr. 2004
  A cyclophane composed of fluorobenzene and phenol units was synthesized in order to observe the C-F...H-O hydrogen bond. In the crystal structure, 20% of the molecule clearly shows the intramolecular hydrogen bond and the other 80% is free from hydrogen bonding. On the other hand, a distinct low-field shift of the phenolic OH proton was observed in the H-1 NMR spectrum compared to that of the F-free analog. Furthermore, O-H...F through-space coupling was observed. From the results of the crystallographic analysis, IR, and NMR spectra, the C-F...H-O hydrogen bond energy of this system was estimated to be 0.84-3.7 kJ.mol(-1). (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).
  WILEY-V C H VERLAG GMBH, English
  DOI：https://doi.org/10.1002/ejoc.200300698
  DOI ID：10.1002/ejoc.200300698, ISSN：1434-193X, CiNii Articles ID：80017044220, Web of Science ID：WOS:000221286100020
• Controlled radical polymerization of vaporized vinyl monomers on solid surfaces under UV irradiation　　　　　　　　　　　　　　　
  M Yasutake; Y Andou; S Hiki; H Nishida; T Endo
  MACROMOLECULAR CHEMISTRY AND PHYSICS, Volume：205, Number：4, First page：492, Last page：499, Mar. 2004
  In order to prepare well-defined polymers on solid surfaces in the gas phase, a gas phase-assisted surface polymerization (GASP) of vinyl monomers was carried out on solid surfaces pre-coated with a photoiniferter, 2-cyanoprop-2-yl N,N'-dimethyldithio,carbamate, under UV irradiation. The GASP of methyl methacrylate (MMA) resulted in the formation of polymer on the surfaces and showed a proportional relationship between (M) over bar (n) and polymer yield. Consecutive copolymerization of MMA and styrene led to the formation of a block copolymer which was confirmed by a selective solvent fractionation method. These results demonstrate that controlled radical polymerization of vaporized monomer occurred on the solid surfaces.
  WILEY-V C H VERLAG GMBH, English
  DOI：https://doi.org/10.1002/macp.200300089
  DOI ID：10.1002/macp.200300089, ISSN：1022-1352, CiNii Articles ID：80016533689, Web of Science ID：WOS:000220209300010
• Physically controlled radical polymerization of vaporized vinyl monomers on surfaces. Synthesis of block copolymers of methyl methacrylate and styrene with a conventional free radical initiator　　　　　　　　　　　　　　　
  M Yasutake; S Hiki; Y Andou; H Nishida; T Endo
  MACROMOLECULES, Volume：36, Number：16, First page：5974, Last page：5981, Aug. 2003
  Physically controlled radical polymerization of vinyl monomers with conventional free radical initiators was achieved in the presence of monomer vapors on solid substrate surfaces. The polymerization of methyl methacrylate (MMA) and styrene (St) by 2,2'-azobis(isobutyronitrile) (AIBN) on substrate surfaces resulted in the deposition of high molecular weight polymers, forming a rough surface morphology in such forms of aggregated particles. The proportional relationship between the number-average molecular weight and polymer yield was successfully obtained, and the consecutive copolymerization of MMA and St produced a block copolymer, poly(MMA-b-St). These results support the living nature of the free radical polymerization on surfaces in the presence of monomer vapors. The SEM observations of the deposits revealed that the polymerization proceeded with a continuous polymer deposition taking place at points where the active species were immobilized, reflecting a predesigned pattern on the substrate surface.
  AMER CHEMICAL SOC, English
  DOI：https://doi.org/10.1021/ma021795s
  DOI ID：10.1021/ma021795s, ISSN：0024-9297, Web of Science ID：WOS:000184628000016
• Crystal structure of 4,13-dimethyl-3,7,10,14,19,22,25-heptaoxapentacyclo[25.0.0(1,6).0(6,26)0(11,16).0(11,18)]heptacosa-4,11-diene-2,15-dione　　　　　　　　　　　　　　　
  T Shimo; K Uchiyama; M Yasutake; T Shinmyozu; K Somekawa
  ANALYTICAL SCIENCES, Volume：17, Number：8, First page：1017, Last page：1018, Aug. 2001
  JAPAN SOC ANALYTICAL CHEMISTRY, English
  DOI：https://doi.org/10.2116/analsci.17.1017
  DOI ID：10.2116/analsci.17.1017, ISSN：0910-6340, Web of Science ID：WOS:000170499900021
• A potassium complex of a fluorine-containing macrocyclic cage compound: Interactions between fluorine atoms and metal ions　　　　　　　　　　　　　　　
  H Takemura; N Kon; M Yasutake; H Kariyazono; T Shinmyozu; T Inazu
  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Volume：38, Number：7, First page：959, Last page：961, 1999
  WILEY-V C H VERLAG GMBH, English
  DOI：https://doi.org/10.1002/(SICI)1521-3773(19990401)38:7<959::AID-ANIE959>3.0.CO;2-8
  DOI ID：10.1002/(SICI)1521-3773(19990401)38:7<959::AID-ANIE959>3.0.CO;2-8, ISSN：1433-7851, CiNii Articles ID：80011079192, Web of Science ID：WOS:000079641000019

• Recent Advances in Electrochromic Devices　　　　　　　　　　　　　　　
  樋口, 昌芳, [Joint work]
  Jun. 2019
  Japanese, Total pages：vi, 216p
  CiNii Books：http://ci.nii.ac.jp/ncid/BB29176542
  ISBN：9784781314235, CiNii Books ID：BB29176542

• Synthesis of D-A liquid crystalline electrochromic compounds and development of their electrochromic devices　　　　　　　　　　　　　　　
  Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (C), 01 Apr. 2017 - 31 Mar. 2020
  Yasutake Mikio, Saitama University
  Grant amount(Total)：4810000, Direct funding：3700000, Indirect funding：1110000
  We were designed four kinds of liquid crystal materials having pyrendithione and bithiophene moieties and synthesized. And their liquid crystalline properties were also investigated. Furthermore, we investigated the electrochromic properties of PQBTs in the solutions. After, the electrochromic devices using PQBTs were formed, and this was also examined. In particular, the electrochemical properties of PQBTs in solution were better than those previously reported and showed electrochromic properties over a wide range of potentials. In addition, the PQBTs devices showed electrochromic characteristics of three colors. In addition, we also investigated the switching speeds of these and examined their repeatability.
  Grant number：17K05826
• The preparation and behavior of liquid crystal molecules which appear electrochromism by electrochemical oxidation and reduction.　　　　　　　　　　　　　　　
  Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Young Scientists (B), 2011 - 2013
  YASUTAKE Mikio, Saitama University
  Grant amount(Total)：4420000, Direct funding：3400000, Indirect funding：1020000
  Two kinds of liquid crystal compound having an anthraquinone and bithiophene moieties were synthesized. The mesophases exhibited, have been characterized by means of polarized optical microscopy observation (POM), differential scanning calorimetry (DSC), X-ray diffraction (XRD) studies. The observation results, those phase was lamellar phase. Furthermore, those electrochemic properties were examined by cyclic voltammetry (CV). And the electrochromism of the liquid crystal compounds was also examined by UV-vis spectra.Moreover, the electrochromic devices were made and the color property in the electrochemistry was observed.
  Finally mixture of an ionic liquid crystal and an electrochromics material was prepared, and it was examined. However, they caused phase separation.
  Grant number：23750207
• -　　　　　　　　　　　　　　　
  Competitive research funding
• -　　　　　　　　　　　　　　　
  Competitive research funding