著者

Yamamoto Yohei

出版者

公益社団法人 日本化学会

雑誌

Bull. Chem. Soc. Jpn. (ISSN:00092673)

巻号頁・発行日

vol.84, no.1, pp.17-25, 2011

被引用文献数

12

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Self-assembly of &pi;-conjugated molecules is attractive for construction of well-defined, nanometer-scale electroactive materials. This account describes our developments on self-assembled nanotubes from Gemini-shaped hexa-<i>peri</i>-hexabenzocoronenes (HBCs). At first, detailed molecular arrangement in the nanotube is presented, which is perfectly revealed by a synchrotron radiation X-ray diffraction analysis of a macroscopic fiber consisting of highly aligned HBC nanotubes. Next, electroconductive properties of the HBC nanotubes are investigated. By means of direct current and noncontact methods, anisotropic charge-transport properties in the nanotubes are confirmed. The effect of the surface oligoether chains on intertubular conduction is also examined by field-effect transistor measurements. Finally, optoelectronic applications are developed by constructing newly designed nanotubes. These nanotubes possess a coaxial configuration, where an electron-donating graphitic bilayer of &pi;-stacked HBC arrays is laminated by an electron-accepting molecular layer. Due to the molecular-layer donor/acceptor heterojunction, the nanotubes exhibit remarkable photoconduction and photovoltaic outputs. Furthermore, the optoelectronic properties are modulated by changing the density of electron acceptors on the nanotube surfaces by coassembly of multiple components or utilizing photochromism. These results will advance to electronic and optoelectronic applications of supramolecular nanomaterials.

著者

Yasuyuki Takeda Koji Katsuta Yoshihisa Inoue Tadao Hakushi

出版者

The Chemical Society of Japan

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.61, no.3, pp.627-632, 1988 (Released:2006-06-27)

参考文献数

41

被引用文献数

41

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Conductivities of alkali metal salts in the presence of 15-crown-5 (15C5), 16-crown-5 (16C5), and benzo-15-crown-5 (B15C5) were measured at 25 °C in acetonitrile, propylene carbonate, and methanol. Formation constants (KML+) of 1:1 complexes of 15C5 and 16C5 with alkali metal ions and conductance parameters (λ0 and å) of the Na+ complexes of 15C5, 16C5, and B15C5 were determined, λ0 and å being limiting ionic molar conductivity and distance of closest approach of ions, respectively. In general, selectivities of 15C5 and 16C5 for alkali metal ions show the size-fit correlation. In contrast to 15C5, 16C5 forms much the most stable complex with Na+ in every solvent. Generally, KML+-value sequences of a given crown ether complex for the solvents are the reverse of donor-number sequences of the solvents. Value of å increases with an increase in the cationic size (Na+→Na(15C5)+→Na(16C5)+→Na(B15C5)+). Mobility of the Na+–crown ether complex decreases with an increase in the size of the crown ether. From λ0 values and Walden products of these Na(crown ether)+ complexes and a tetrapropylammonium ion, it seems likely that Na(15C5)+ and Na(16C5)+ act as structure breakers in hydrogen-bonding solvents, whereas Na(B15C5)+ as a structure maker.

著者

Chapyshev Sergei Victorovich Tomioka Hideo

出版者

公益社団法人 日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.76, no.11, pp.2075-2089, 2003-11-15

参考文献数

47

被引用文献数

49

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Photochemical transformations of quintet dinitrenes have been studied for the first time by FTIR spectroscopy during the photolysis of 1,3-diazidobenzene and its 2-methyl- and 2,4,6-trimethyl-substituted derivatives in solid argon at 13 K. The reactions involve two competitive processes. In the first one, the intramolecular insertion of the nitrene unit into the 1,6-aromatic bond induces ring-opening, which leads to the formation of aminoacetylenes. The second process involves the intramolecular addition of the nitrene unit to the 1,2-aromatic bond followed by ring-opening to form 4(2<I>H</I>-azirin-2-ylidene)-2-butenenitrile derivatives. Methyl groups in <I>ortho</I>-positions to the nitrene units of quintet dinitrenes efficiently protect their aromatic ring from nitrene attacks, substantially increasing the photochemical stability of such species. However, even quintet 2,4,6-trimethylphenylene-1,3-dinitrene decomposes to ring-opened products on extended irradiation. This indicates that quintet dinitrenes are much more photochemically reactive species than triplet nitrenes. Undesirable photochemical rearrangements of the latter at early stages of the photolysis of 1,3-diazidobenzenes are suppressed on introducing the methyl group in position 2 of these azides.

著者

Taketo Kojima Ikumi Kawajiri Jun-ichi Nishida Chitoshi Kitamura Hiroyuki Kurata Mirai Tanaka Hiroshi Ikeda Takeshi Kawase

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

pp.20160093, (Released:2016-05-24)

被引用文献数

8

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A series of 2,3-diphenylphenanthro[9,10-b]furans were prepared by the reactions of phenanthrene-9,10-dione with two equivalents of benzylidenetriphenylphosphoranes as a key step. The bis(4-bromophenyl) derivative can be readily lithiated by the action of n-butyllithium in diethyl ether. The corresponding 4-trimethylsilyl and 4-methylthio derivatives were obtained by quenching the dilithio derivative with trimethylsilyl chloride and dimethyl disulfide, respectively. The Buchwald–Hartwig amination of the bromide with diphenylamine afforded the diphenylamino derivative in a good yield. Crystallographic analysis of the parent diphenyl derivative reveals that the phenanthrofuran moiety has a slightly twisted helicene-like structure, and the compound forms a columnar stacking in the crystal. The phenanthrofurans display intense blue fluorescence both in CH2Cl2 and in the solid state. Their electrochemical properties obviously indicate high HOMO energy levels of the furans, as predicted by the density functional theory calculations.

著者

Takasuke Mukaiyama Tadafumi Uchimaru Yujiro Hayashi

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.89, no.4, pp.455-459, 2016-04-15 (Released:2016-04-15)

参考文献数

80

被引用文献数

2

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The stability of E/Z-alkoxyenamines from α-alkoxyaldehyde with pyrrolidine was discussed by conducting density functional theory (DFT) calculations with natural bond orbital (NBO) analysis.

著者

Shigenori Nagatomo Megumi Nobuhira Yasuhisa Yamamura Masato Sumita Kazuya Saito

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.86, no.5, pp.569-576, 2013-05-15 (Released:2013-05-15)

参考文献数

31

被引用文献数

8

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Nonmonotonous temperature dependence, which suggests formation of closed oligomer(s) via hydrogen-bonds, is detected in heat capacity and dielectric constant of the title compound in the liquid state. The 1H NMR signal of hydroxy protons showed a temperature-dependent fine structure. Quantum-chemical calculations on oligomers of several types revealed that the fine structure is plausibly interpreted as a temperature-dependent formation/destruction of oligomers. A coherent analysis of calorimetric, FT-IR, dielectric, and 1H NMR results shows that the neat liquid of the title compound consists mostly of closed (square) tetramers via H-bonds at lower temperatures, and oligomers with open (or straight) H-bonding and non-H-bonding (monomer) at higher temperature.

著者

Shinji Toyota Takao Yamamori Mitsuhiro Asakura Michinori Oki

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.73, no.1, pp.205-213, 2000 (Released:2001-10-31)

参考文献数

37

被引用文献数

28

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The substituent effect on the rotational barriers of acetylenic to tetrahedral C-C bonds was studied for the title compounds carrying Me or OMe substituents at the 1,4-positions in the 9-triptycyl groups. These compounds were prepared by use of the Diels-Alder and the Sonogashira reactions from a 9-ethynylanthracene derivative. The kinetic parameters were determined by the total lineshape analysis of the signals observed by the variable temperature 1H NMR for five compounds. The rotational barriers are in the range of 9—15 kcal mol-1, and are enhanced as the steric size of the substituents is increased (H < OMe < Me). This substituent effect is attributed to the destabilization of the transition state of the rotation process, where the two triptycyl groups are almost eclipsed about the central axis, by the steric interactions between the peri substituents. The acetylenic carbons are significantly deformed from the linear geometry in the X-ray structure of the tetramethyl compound. The substituent effect on the rotamer population is also discussed with the aid of the MM calculation.

著者

Shoichi Nakano

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.29, no.2, pp.219-224, 1956 (Released:2006-04-12)

参考文献数

20

被引用文献数

4 3

著者

Jing-Dong Guo Takahiro Sasamori Yutaro Yamamoto Hiroshi Matsubara Shigeru Nagase Hideki Yorimitsu

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

pp.20150343, (Released:2015-11-16)

被引用文献数

4

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The previously reported palladium-catalyzed silylation of aryl chlorides with silylsilatranes were theoretically reinvestigated by DFT calculations with a focus on the effect of the transannular Si–N coordination on silyl transfer. The Si–N coordination proved to be not so influential as to accelerate the silyl transfer. However, it should be of benefit to use silylsilatranes as silylating agents because of their easy handling and facile preparation.

著者

Naoki Aratani Atsuhiro Osuka

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.1, pp.1-27, 2015-01-15 (Released:2015-01-15)

参考文献数

241

被引用文献数

35 1

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Directly linked linear porphyrin arrays were synthesized and their photophysical properties depending on the length of the arrays were investigated. Ag(I)-promoted oxidative coupling of 5,15-diaryl Zn(II) porphyrins has proven to be effective for preparations of very long meso–meso-linked Zn(II) porphyrin arrays (Zn). A stepwise doubling strategy with strict purification at each doubling step allowed for preparation of gigantic but discrete linear arrays in an unprecedented manner. Large cyclic porphyrin wheels were also synthesized by final meso–meso coupling intramolecular cyclization. Crucial to this success are high reactivity and high regioselectivity of the Ag(I)-promoted oxidative coupling. Equally important are high solubilities of Zn despite their large molecular weights, which arise from their perpendicularly linked structures. Another advantage of this doubling strategy is a large difference in the molecular weights among reactants and products that increases as the reactant array becomes larger, allowing separation of coupling products by preparative GPC-HPLC. As an alternative protocol, Pd-catalyzed Suzuki–Miyaura cross-coupling has been extensively used for synthesis of cyclic porphyrin arrays. This strategy gave novel linear and cyclic porphyrin arrays from β-borylated porphyrins that were prepared by Ir-catalyzed borylation of meso-free porphyrins. As an interesting example, a porphyrin nanotube consisting of four porphyrins doubly bridged by 2,6-pyridinylene spacers was synthesized and revealed to possess a C60-encapsulation capability. Exciton coupling, effective energy hopping, coherent length, and excitation energy transfer of meso–meso-linked linear and cyclic porphyrin arrays are discussed. STM and AFM detections of the large porphyrin arrays are also presented. We believe that these studies expand the range of organic molecules we can manipulate and open a door to a new area of nanoscaled and sub-microscaled functional porphyrin materials.

著者

Ken Tanaka Yuki Kimura Koichi Murayama

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.3, pp.375-385, 2015-03-15 (Released:2015-03-15)

参考文献数

112

被引用文献数

113 5

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The highly enantioselective synthesis of functionalized helicenes and helicene-like molecules have been achieved via rhodium-catalyzed [2+2+2] cycloaddition reactions. The rhodium-catalyzed enantioselective intramolecular [2+2+2] cycloaddition of 2-naphthol-linked triynes afforded [7]helicene-like molecules in good yields and ee values. The more sterically encumbered reaction, the rhodium-catalyzed enantioselective double intramolecular [2+2+2] cycloaddition of a 2-naphthol-linked hexayne, also proceeded to give a [11]helicene-like molecule with high ee value, although the product yield was low. Not only intramolecular cycloaddition reactions but also intermolecular ones were accomplished by combinations of electron-rich tetraynes and electron-poor diynes to give [7]- and [9]helicene-like molecules and [7]helicenes in varying yields and ee values.

著者

Yoshiki Chujo Kazuo Tanaka

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.5, pp.633-643, 2015-05-15 (Released:2015-05-15)

参考文献数

45

被引用文献数

301 11

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The concept and representative examples of “element-block polymers” are described. A structural unit consisting of various groups of elements is called an “element-block.” In this review, unique properties of “element-block polymers” composed of organoboron complexes, o-carboranes, and polyhedral oligomeric silsesquioxanes as typical examples of element blocks are illustrated. The design and synthesis of new element-blocks and development of methods forming higher-order structures for realizing the desired functions based on a bottom-up approach are explained.

著者

Sarah A. Weicker Douglas W. Stephan

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.8, pp.1003-1016, 2015-08-15 (Released:2015-08-15)

参考文献数

107

被引用文献数

100

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The advent of frustrated Lewis pair (FLP) chemistry almost a decade ago was based on the reactivity of sterically encumbered combinations of electrophilic boranes and phosphines with hydrogen. Since that time the chemistry has broadened dramatically in terms of reactivity and applications. Nonetheless, the majority of the work has continued to exploit the borane B(C6F5)3. In this review, we describe FLP chemistry that has developed by employing alternatives to this Lewis acid. Lewis acids derived from group 13, 14, and 15 based systems are described, thus demonstrating a growing area in the main group reactivity based on FLPs.

著者

Atsushi Wakamiya Shigehiro Yamaguchi

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.10, pp.1357-1377, 2015-10-15 (Released:2015-10-15)

参考文献数

179

被引用文献数

218

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Boron, a group 13 element, has several characteristic structural and electronic features: 1) trivalent boron compounds usually adopt a trigonal planar geometry; 2) due to the presence of a vacant p-orbital, effective orbital interaction with π-conjugated compounds is possible; 3) the presence of a vacant p-orbital is furthermore responsible for high Lewis acidity; 4) the boryl group acts as a π-electron-accepting group particularly in the excited state. The consequent exploitation of these characteristic features of boron in the molecular design enables us to produce sophisticated π-functional materials with attractive photophysical and electronic properties. This account article illustrates our systematic studies on the molecular design and the development of functional π-electron materials using boron as a key element.

著者

Kazuhiko Takai

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.11, pp.1511-1529, 2015-11-15 (Released:2015-11-15)

参考文献数

133

被引用文献数

8

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During the development of new synthetic organic reactions by the use of group 4–7 metals, we twice encountered a reproducibility problem. The key factor was trace amounts of second metal elements that contaminated the first, main metals, i.e., nickel in chromium and lead in zinc. We had determined the standard procedures for these reactions and they were adopted in Organic Syntheses. The difference in the source of zinc, i.e., contamination by a catalytic amount of lead, proved to affect both the reactivity of the Simmons–Smith reaction and the formation of alkylzinc from the corresponding iodides. By using the concept of catalytic effects of the second metals, we developed a method to use manganese metal and applied this to sequential radical and anionic reactions. In addition, allylic aluminum species were prepared smoothly from allylic halides and aluminum by addition of an indium salt, the second element. In this account, I describe how the synthetic methods were discovered and developed, with an emphasis on the stories behind the communications and articles.

著者

Kanji Miyabe Youki Shimazaki

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

pp.20150203, (Released:2015-08-25)

被引用文献数

12

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We developed a capillary electrophoretic (CE) method for the kinetic study of intermolecular interactions. Neither immobilization nor chemical modification, e.g., fluorescence labelling, of solute and ligand molecules is required. A concept of chromatographic capillary electrophoresis (CCE) was introduced as an experimental CE procedure. In the CCE mode, the migration of solute-ligand complex in a capillary is stopped. Only solute molecule migrates and is detected. New moment equations were developed, which were essential for determining association and dissociation rate constants from elution peak profiles measured under the CCE conditions. The combination of the CCE concept and the moment theory leads to the CE method, i.e., moment analysis by CCE (MACCE). However, because it was hard to really perform CE experiments under the CCE conditions, we also developed practical experimental and data analysis procedures for the MACCE measurement. The reaction rate constants were analytically determined by the MACCE method for the formation and dissociation of the inclusion complex between thymol and sulfated-β-cyclodextrin. It is unnecessary to fit elution curves numerically calculated to those experimentally measured for determining the rate constants. It was demonstrated that the MACCE method was effective for the kinetic study of intermolecular interactions.

著者

Kazuhiko Saigo Naomi Kubota Shoko Takebayashi Masaki Hasegawa

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.59, no.3, pp.931-932, 1986 (Released:2006-06-27)

参考文献数

9

被引用文献数

61

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(±)-1,2-Diphenylethylenediamine (DPEDA) was efficiently resolved by the fractional crystallization of its diastereomeric salts with optically active mandelic acid. 1H-NMR spectrum of N-monoacylated DPEDA with an optically active derivatizing agent showed that DPEDA thus obtained was optically pure.

著者

Takaya Hikaru Nakajima Sho Nakagawa Naohisa Isozaki Katsuhiro Iwamoto Takahiro Imayoshi Ryuji Gower Nicholas J. Adak Laksmikanta Hatakeyama Takuji Honma Tetsuo Takagaki Masafumi Sunada Yusuke Nagashima Hideo Hashizume Daisuke Takahashi Osamu Nakamura Masaharu

出版者

Chemical Society of Japan

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.3, pp.410-418, 2015

被引用文献数

39

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放射光施設SPring-8で鉄触媒の作用を直接観察. 京都大学プレスリリース. 2015-03-16.

著者

Masahiko Takahashi

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.82, no.7, pp.751-777, 2009-07-15 (Released:2009-07-10)

参考文献数

193

被引用文献数

77

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Over the last four decades an experimental method has been developed for looking at electron orbitals in momentum space. The method, called electron momentum spectroscopy (EMS), is based on the electron-impact ionizing reaction near the Bethe ridge at incident electron energies of the order of 1 keV or higher. This account reviews frontiers of the field, involving the first approach to molecular frame EMS that enables one to look at molecular orbitals in three-dimensional form.

著者

Naoki Imazu Tsuyohiko Fujigaya Naotoshi Nakashima

出版者

(社)日本化学会

雑誌

Bulletin of the Chemical Society of Japan (ISSN:00092673)

巻号頁・発行日

vol.88, no.1, pp.217-221, 2015-01-15 (Released:2015-01-15)

参考文献数

35

被引用文献数

10

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To fabricate transparent conducting films (TCFs) for electronic devices, both a high conductivity and thermal stability are significant issues due to the need for a high temperature annealing process. In this report, we describe the preparation of a highly transparent (94% transmittance), conductive (surface resistivity: 354 Ω sq−1) and thermally stable double-walled carbon nanotube (DWCNT) film without adding any chemical doping or rinsing. Such film was obtained by a simple dilution and condensation/filtration process (DC/F). The procedure is quite simple, and thus large scalability is easy.