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奥島 鉄雄オクジマ テツオ

所属部署
大学院理工学研究科 環境機能科学専攻
職名准教授
メールアドレス
ホームページURLhttp://chem.sci.ehime-u.ac.jp/~orgchem1/index.html
生年月日
Last Updated :2018/05/25

研究者基本情報

学位

  • 博士(理学)

経歴

  •   2011年01月, 愛媛大学大学院理工学研究科, 准教授
  •   2007年04月,  - 2010年12月, 愛媛大学大学院理工学研究科, 助教
  •   2006年04月,  - 2007年03月, 愛媛大学, 特任講師
  •   2006年04月,  - 2007年03月, 愛媛大学大学院理工学研究科, 助手
  •   2002年10月,  - 2006年03月, 愛媛大学理学部, 助手
  •   2002年04月,  - 2002年09月, 東北大学大学院理学研究科化学専攻, 技術補佐員

所属学協会

  • ポルフィリンフタロシアニン学会
  • 有機合成化学協会
  • 応用物理学会
  • 基礎有機化学会
  • 日本化学会

研究活動情報

研究分野

  • 有機化学

研究キーワード

    有機合成, 芳香族化合物, ポルフィリン, フタロシアニン, アズレン, 有機電界効果トランジスタ, 有機薄膜太陽電池, 構造有機化学

論文

  • Synthesis of 2-amino- and 2-arylazoazulenes via nucleophilic aromatic substitution of 2-chloroazuelenes with amines and arylhydrazines
    奥島 鉄雄, Org. Biomol. Chem., 15, 3917 - 3923,   2017年
  • Synthesis and Electrochemical Properties of Azulene-Substituted Tetracyanobutadiene and Dicyanoquinodimethane Chromophores Connected with Naphthalene Cores
    奥島 鉄雄, Heterocycles , 95, 353 - 369,   2017年
  • Diethyl N,N’-dimethylpyrrol[3,4-f]isoindole-1,7-dicarboxylate as a 14-electronic aromatic compound with two azomethine-ylide moieties
    平岡尚悟; 田原寛之; 森 重樹; 奥島鉄雄; 髙瀬雅祥; 中江隆博; 宇野英満*, Tetrahedron , 73, 957 - 963,   2017年
  • Protonation Behavior of Thiaporphyrin and Thiabenzoporphyrin
    田川和成; 森 重樹; 奥島鉄雄; 髙瀬雅祥; 宇野英満*, Tetrahedron, 73, 794 - 801,   2017年
  • One-pot Synthesis of a Rice Ball-shaped Cyclophane with syn-Diethanoanthracene-fused Dipyrrole and Hexafluorobenzene
    沖 光脩; 田川和成; 森 重樹; 髙瀬雅祥; 奥島鉄雄; 宇野英満*, Chem. Lett. , 46, 243 - 244,   2017年
  • Synthesis of hexagonal shape-persistent cyclophane with D2h symmetry
    田川和成; 森 重樹; 髙瀬雅祥; 奥島鉄雄; 久木一朗; 宇野英満*, Tetrahedron Lett. , 57, (36) ,   2016年
  • Synthesis, Characterization and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
    奥島鉄雄*; Mack, John*;中村 純; Kubheka, Gugu; Nyokong, Tebello; Zhu, Hua; 菰渕直樹; 小野 昇; 山田容子; 宇野英満; 小林長夫*, Chem. Eur. J. , 22, (41) ,   2016年
  • Syntheisi of 1,2’-Biazulenes by Palladium-Catalyzed Unusual Homocoupling Reaction of 1-Haloazulenes in the presence of Ferrocene
    庄子 卓*; Miyashita, Kanami; Araki, Takanori; 丸山晃史; Sekiguchi, Ryuta; 伊東俊司; 奥島鉄雄, Synthesis , 48, (15) ,   2016年
  • Template Synthesis of Decaphyrin without Meso-Bridges: Cyclo[10]pyrrole
    奥島鉄雄*;安藤千恵; Agrawal, Saurabh; 松本宏樹; 森 重樹; 小原敬士; 久木一朗; 中江隆博; 髙瀬雅祥; 宇野英満; 小林長夫*, J. Am. Chem. Soc., 138, (24) 7540 - 7543,   2016年
  • Synthesis of cyclo[8]pyrrole–polyoxometalate double-decker complex
    奥島鉄雄*; 松本宏樹; 森 重樹; 中江隆博; 髙瀬雅祥; 宇野英満, Tetrahedron Lett. , 57, (29) ,   2016年
  • Synthesis and Properties of (3-Phenyl-1-azulenyl)tetracyanobetadienes and Tris(aryltetracyanobetadiene)s Connected with 1,3,5-Tri(1-azulenyl)benzene Core
    Chemistry Select, 1, 49 - 56,   2016年
  • 4,8-Dihydropyrrol[3,4-f]isoindole as a Useful Building Block for Near-Infrared Dyes
    *宇野英満; 中村光則; 上代一貴; 森 重樹; 奥島鉄雄, Heterocycles, 90, (2) 1158 - 1167,   2015年01月01日
  • Synthesis and Properties of (3-Phenyl-1-azulenyl)tetracyanobetadienes and Tris(aryltetracyanobetadiene)s Connected with 1,3,5-Tri(1-azulenyl)benzene Core
    *庄子 卓; 丸山晃史; Tanaka, Miwa; 永井大地; 下村えりか; 藤森邦秀; 伊東俊司; 奥島鉄雄; 豊田耕三; 安並正文(the late), Chemistry Select , 1, 49 - 56,   2015年
  • Synthesis of 2- and 6-thienylazulenes by palladium-catalyzed direct arylation of 2- and 6-haloazulenes with thiophene derivatives
    *庄子 卓; 丸山晃史; Araki, Takanori; 伊東俊司; 奥島鉄雄, Org. Biomol. Chem., 13, (40) 10191 - 10197,   2015年
  • Synthesis, Properties and Redox Behavior of Ferrocenyl-1,1,4,4-tetracyano-1,3-butadienes Connected by Arylamine and Azobenzene Spacers
    *庄子 卓; 鎌田夏美; 丸山晃史; 伊東俊司; 奥島鉄雄, Bull. Chem. Soc. Jpn., 88, (9) 1338 - 1346,   2015年
  • Synthesis, Properties, and Redox Behavior of Tris(1-azulenyltetracyanobutadiene) and Tris[1-azulenylbis(tetracyanobutadiene)] Chromophores Connected to a 1,3,5-Tri(1-azulenyl)benzene Core
    *庄子 卓; 丸山晃史; 下村えりか; 永井大地; 伊東俊司; 奥島鉄雄; 豊田耕三, Eur. J. Org. Chem., 2015, (9) 1979 - 1990,   2015年
  • Synthesis, Properties, and Redox Behavior of 1,1,4,4-Tetracycano-2-ferrocenyl-1,3-butadienes Connected by Aryl, Biaryl, and Teraryl Spacers
    *庄子 卓; 丸山晃史; 夜久千紗; 鎌田夏美; 伊東俊司; 奥島鉄雄; 豊田耕三, Chem. Eur. J., 21, (1) 402 - 409,   2015年
  • Preparation, characterization, and cycloaddition reaction of the heterocumulenes attached directly to azulenes. An efficient strategy for the preparation of azulene-substituted heterocycles
    伊東俊司*; 奥島鉄雄; 甲千寿子; 森田 昇, Tetrahedron Symposia-in-Print, 59, (25) 4651 - 4659,   2003年
  • Preparation and Stille cross-coupling reaction of the first organotin reagents of azulenes. Easy access to poly(azulen-6-yl)benzene derivatives
    伊東俊司*; 奥島鉄雄; 森田 昇, Journal of the Chemical Society. Perkin Transactions. 1, (16) 1896 - 1905,   2002年
  • Preparation and Stille cross-coupling reaction of the first organotin reagents of azulenes. An efficient Pd(0)-catalyzed synthesis of 6-aryl- and biazulenes
    奥島鉄雄; 伊東俊司*; 森田 昇, Tetrahedron Letters, 43, (7) 1261 - 1264,   2002年
  • Synthesis and Redox Behavior of Azulene-Substituted Benzene Derivatives and (5-Cyclopentadienyl)[tetra- and di(6-azulenyl)cyclobutadiene]cobalt Complexes
    伊東俊司*; 稲部陽樹; 奥島鉄雄; 森田 昇; 渡部政隆; 原田宣之; 今福公明, Journal of Organic Chemistry, 66, (21) 7090 - 7101,   2001年
  • Synthesis, Properties, and Redox Behavior of Di(1-azulenyl)(2- and 3-thienyl)methyl Cations and Dications Composed of Two Di(1-azulenyl)methylium Units Connected with 2,5-Thiophenediyl and 2,5-Thienothiophenediyl Spacers
    伊東俊司*; 菊池 茂; 奥島鉄雄; 森田 昇; 浅尾豊信, 66, (7) 2470 - 2479,   2001年
  • Reaction of 2-Aminoazulenes with Aldehydes. One Pot Synthesis of Diazuleno[2,1-b:1,2-e]pyridines
    奥島鉄雄; 寺園友美; 伊東俊司*; 森田 昇*; 浅尾豊信, 54, 667 - 678,   2001年
  • Synthesis and redox behavior of 1,3,5- and 1,2,4-tri(6-azulenyl)benzene derivatives
    伊東俊司*; 稲部陽樹; 奥島鉄雄; 森田 昇; 渡部政隆; 原田宣之; 今福公明, Tetrahedron Letters, 42, (6) 1085 - 1089,   2001年
  • Diels-Alder approach to the synthesis of azulene-substituted benzene derivatives. Synthesis and redox behavior of 1,2-di(6-azulenyl)tetraphenylbenzenes
    伊東俊司*; 稲部陽樹; 奥島鉄雄; 森田 昇; 渡部政隆; 今福公明, Tetrahedron Letters, 41, (43) 8343 - 8347,   2000年
  • 1,1-Ethylene-1H-azulenium Ion and Its Alkyl Substituted Derivatives: Synthesis, Characterization, and Some Reactions Thereof
    小田晃規*; 梶岡孝則; 内山拓弥; 永良弘毅; 奥島鉄雄; 伊東俊司; 森田 昇*; 佐藤年男; 宮武竜太; 黒田重靖*, Tetrahedron Symposia-in-Print, 55, (19) 6081 - 6096,   1999年
  • Generation, Characterization and Some Reaction of 1,1-Ethylene-1H-azulenium Ion
    小田晃規*; 梶岡孝則; 奥島鉄雄; 伊東俊司; 森田 昇; 宮武竜太; 黒田重靖*, (10) 1011 - 1012,   1997年

MISC

  • Strain-induced skeletal rearrangement of a polycyclic aromatic hydrocarbon on a copper surface
    Akitoshi Shiotari, Takahiro Nakae, Kota Iwata, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno, Hiroshi Sakaguchi, Yoshiaki Sugimoto, Yoshiaki Sugimoto, Nature Communications, 8,   2017年07月20日, Controlling the structural deformation of organic molecules can drive unique reactions that cannot be induced only by thermal, optical or electrochemical procedures. However, in conventional organic synthesis, including mechanochemical procedures, it is difficult to control skeletal rearrangement in polycyclic aromatic hydrocarbons (PAHs). Here, we demonstrate a reaction scheme for the skeletal rearrangement of PAHs on a metal surface using high-resolution noncontact atomic force microscopy. By a combination of organic synthesis and on-surface cyclodehydrogenation, we produce a well-designed PAH - diazuleno[1,2,3-cd:1′,2′,3′-fg]pyrene - adsorbed flatly onto Cu(001), in which two azuleno moieties are highly strained by their mutual proximity. This local strain drives the rearrangement of one of the azuleno moieties into a fulvaleno moiety, which has never been reported so far. Our proposed thermally driven, strain-induced synthesis on surfaces will pave the way for the production of a new class of nanocarbon materials that conventional synthetic techniques cannot attain.
  • Synthesis of 2-Aminofurans by Sequential [2+2] Cycloaddition–Nucleophilic Addition of 2-Propyn-1-ols with Tetracyanoethylene and Amine-Induced Transformation into 6-Aminopentafulvenes
    Taku Shoji, Daichi Nagai, Miwa Tanaka, Takanori Araki, Akira Ohta, Ryuta Sekiguchi, Shunji Ito, Shigeki Mori, Tetsuo Okujima, Chemistry - A European Journal, 23,   2017年04月11日, © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Synthesis of 2-aminofuran derivatives with an azulene or N,N-dimethylanilino substituent was established by the formal [2+2] cycloaddition–retroelectrocyclization of 3-(1-azulenyl or N,N-dimethylanilino)-2-propyn-1-ols with tetracyanoethylene, followed by intramolecular nucleophilic addition to the initially formed tetracyanobutadiene moiety of the internal hydroxyl group that come from 2-propyn-1-ol. The reaction proceeds under mild conditions with short reaction period. The products of the reaction are readily available through a simple purification procedure. 2-Aminofuran derivatives obtained by this reaction could be converted into 6-aminofulvene derivatives upon reaction with various amines. The structures of 2-aminofuran and 6-aminopentafulvene with a N,N-dimethylanilino substituent were confirmed by single-crystal X-ray structural analysis.
  • Synthesis of 2-Azulenyltetrathiafulvalenes by Palladium-Catalyzed Direct Arylation of 2-Chloroazulenes with Tetrathiafulvalene and Their Optical and Electrochemical Properties
    Taku Shoji, Takanori Araki, Shuhei Sugiyama, Akira Ohta, Ryuta Sekiguchi, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Journal of Organic Chemistry, 82,   2017年02月03日, © 2017 American Chemical Society. Tetrathiafulvalene (TTF) derivatives with 2-azulenyl substituents 5-11 were prepared by the palladium-catalyzed direct arylation reaction of 2-chloroazulenes with TTF in good yield. Photophysical properties of these compounds were investigated by UV-vis spectroscopy and theoretical calculations. Redox behavior of the novel azulene-substituted TTFs was examined by using cyclic voltammetry and differential pulse voltammetry, which revealed their multistep electrochemical oxidation and/or reduction properties. Moreover, these TTF derivatives showed significant spectral change in the visible region under the redox conditions.
  • Synthesis of azulene-substituted tetraarylpyrroles by reaction of 1-azulenyl ketones with benzoin and ammonium acetate
    Taku Shoji, Sho Takagaki, Miwa Tanaka, Takanori Araki, Shuhei Sugiyama, Ryuta Sekiguchi, Akira Ohta, Shunji Ito, Tetsuo Okujima, Heterocycles, 94,   2017年01月01日, © 2017 The Japan Institute of Heterocyclic Chemistry. Tetraarylpyrroles with a 1-azulenyl substituent were prepared by the reaction of 1-azulenyl ketones, which have various aryl-substituents at their á-position, with benzoin in the presence of ammonium acetate as a nitrogen source of the pyrrole ring. Optical property of the tetraarylpyrroles obtained by the reaction was clarified by UV/Vis spectroscopy and/or time-dependent density functional theory (TD-DFT) calculations.
  • Diethyl N,N′-dimethylpyrrol[3,4-f]isoindole-1,7-dicarboxylate as a 14π-electronic aromatic compound with two azomethine-ylide moieties
    Shogo Hiraoka, Hiroyuki Tahara, Shigeki Mori, Tetsuo Okujima, Masayoshi Takase, Takahiro Nakae, Hidemitsu Uno, Tetrahedron, 73,   2017年01月01日, © 2017 Elsevier Ltd Parikh–Doering oxidation of diethyl 9-hydroxy-2,6-dimethyl-4,8-dihydro-4,8-methanopyrrol[3,4-f]isoindole-1,7-dicarboxylate produced diethyl 9-oxo-2,6-dimethyl-4,8-dihydro-4,8-methanopyrrol[3,4-f] isoindole-1,7-dicarboxylate. This carbonyl derivative spontaneously underwent cheletropic extrusion of carbon monoxide, producing diethyl 2,6-dimethylpyrrol[3,4-f]isoindole-1,7-dicarboxylate, which showed 14π-electronic aromaticity on the whole five-six-five ring system.
  • Synthesis of 2-amino- and 2-arylazoazulenes: Via nucleophilic aromatic substitution of 2-chloroazulenes with amines and arylhydrazines
    Taku Shoji, Shuhei Sugiyama, Takanori Araki, Akira Ohta, Ryuta Sekiguchi, Shunji Ito, Shigeki Mori, Tetsuo Okujima, Masafumi Yasunami, Organic and Biomolecular Chemistry, 15,   2017年01月01日, © 2017 The Royal Society of Chemistry. The S N Ar reaction of 2-chloroazulene derivative 1 with ethoxycarbonyl groups at the 1,3-positions of the azulene ring with several amines afforded the corresponding 2-aminoazulenes 3-9 in excellent yields. 2-Chloroazulene (2) without the electron-withdrawing groups reacted with highly nucleophilic cyclic amines (i.e., morpholine, piperidine and pyrrolidine) under the high-temperature conditions in a sealed tube to produce the corresponding 2-aminoazulenes 10-12 in good yields. 2-Aminoazulenes 10-14 without the electron-withdrawing groups were also obtained in good yields by the treatment of compounds 3-7 with 100% H 3 PO 4 , but in the cases of the reaction of 8 and 9 with a secondary amine function, the decomposition of the products resulted. The synthesis of 2-arylazoazulenes 15-18 was also established via the S N Ar reaction of 1 with arylhydrazines. The optical and electrochemical properties of the 2-arylazoazulene derivatives were examined by UV/Vis spectroscopy, theoretical calculations and voltammetric experiments.
  • Synthesis of 1,2′-Biazulenes by Palladium-Catalyzed Unusual Homocoupling Reaction of 1-Haloazulenes in the Presence of Ferrocene
    Taku Shoji, Taku Shoji, Kanami Miyashita, Takanori Araki, Miwa Tanaka, Akifumi Maruyama, Ryuta Sekiguchi, Shunji Ito, Tetsuo Okujima, Synthesis (Germany), 48,   2016年08月01日, The synthesis of 1,2′-biazulenes was established by palladium-catalyzed homocoupling reactions of the corresponding 1-haloazulenes in the presence of ferrocene. The optical properties of the novel 1,2′-biazulenes were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behaviors of 1,2′-biazulenes were also examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV).
  • Synthesis of hexagonal shape-persistent cyclophane with D2hsymmetry
    Kazunari Tagawa, Shigeki Mori, Masayoshi Takase, Tetsuo Okujima, Ichiro Hisaki, Hidemitsu Uno, Tetrahedron Letters, 57,   2016年01月01日, © 2016 Elsevier Ltd In this study, hexagonal shape-persistent cyclophane with D 2h symmetry and rigid dihedral angles was obtained through the key S N Ar reaction of perfluorobenzene moieties and dipyrroles. The X-ray analysis of the compound thus obtained revealed a hexagonal macrocyclic structure with D 2h symmetry due to the dihedral angles of 120° and double 120° for bicyclo[2.2.2]octadiene-fused dipyrrole and syn-diethanotetrahydroanthracene-fused dipyrrole, respectively.
  • Synthesis, properties, and redox behavior of 1,1,4,4-tetracyano-2-ferrocenyl-1,3-butadienes connected by aryl, biaryl, and teraryl spacers
    Taku Shoji, Taku Shoji, Akifumi Maruyama, Chisa Yaku, Natsumi Kamata, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Chemistry - A European Journal, 21, (1) 402 - 409,   2015年01月02日, © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Aryl-substituted 1,1,4,4-tetracyano-1,3-butadienes (FcTCBDs) and bis(1,1,4,4-tetracyanobutadiene)s (bis- FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro-electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis-FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi-electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions.
  • Synthesis of a Porphyrin-Fused π-Electron System
    Hidemitsu Uno, Kazunari Tagawa, Hajime Watanabe, Naoki Kawamoto, Mina Furukawa, Tetsuo Okujima, Shigeki Mori, Chemical Science of Electron Systems,   2015年01月01日, © Springer International Publishing Switzerland 2015. Oligoporphyrins with a large fused π-electron system were successfully synthesized by the fusion of porphyrin chromophores with polycyclic aromatic hydrocarbons (PAHs). Oligoporphyrins fused with benzene units and zinc diporphyrins fused with PAHs were prepared and their electronic properties were examined. Electronic spectra showed strong absorption in the red to near-infrared (NIR) region. Not only the absorption maxima but also the number of absorption bands was affected by the fusion mode of the porphyrin chromophores. In the UV-vis spectra of the oligoporphyrins, three major absorption bands corresponding to Soret and Q bands were observed. A linearly fused trizinc triporphyrin with two benzene moieties showed strong Q-band absorption at 680nm, while split Q-band absorptions at 663 and 674nm were observed in the L-shaped triporphyrin. Preparation based on the retro-Diels-Alder reaction of the precursors with a bicyclo[2.2.2]octadiene skeleton did not give naphthacene- and pentacene-fused diporphyrins but instead gave naphthalene-, anthracene-, and chrysene-fused diporphyrins. In the chrysene-fused diporphyrin, the absorption maximum in the Q band was 624nm, which was similar to that of naphthalene-fused diporphyrin.
  • Face-and regioselectivity in electrophilic phenylsulfenylation of 7-tert-butoxybicyclo[2.2.1]hepta-2,5-dienes
    Hidemitsu Uno, Masaki Yoshino, Aya Seike, Shigeki Mori, Takahiro Nakae, Takahiro Nakae, Tetsuo Okujima, Heteroatom Chemistry, 25, (5) 367 - 378,   2014年11月01日, © 2014 Wiley Periodicals, Inc. Electrophilic phenylsulfenylation of syn-7-tert-butoxy-2-phenylsulfonyl-bicyclo[2.2.1] hepta-2,5-diene with phenylsulfenyl chloride yielded a mixture of three simple adducts, two of which were derived by the endo face attack of the phenylsulfenyl cation. In the analogous reaction with the anti derivative, only one adduct with the exo phenylsulfanyl group at the nearer carbon was obtained. This product was derived by the attack of the phenylsulfenyl cation from the exo face followed by the endo attack of a chloride anion at the carbon opposite to the phenylsulfonyl group. The similar reaction of 7-tert-butoxybicyclo[2.2.1] hepta-2,5-diene itself underwent no Wager-Meerwein-type rearrangement or transannular reaction, and simple adducts were formed in good combined yield. The combined yield of the products reacted at the syn double bond was ca. 80%.
  • Yellow NIR dye: π-fused bisbenzoBODIPYs with electron-withdrawing groups
    Mitsunori Nakamura, Manami Kitatsuka, Kohtaro Takahashi, Toshi Nagata, Toshi Nagata, Shigeki Mori, Daiki Kuzuhara, Tetsuo Okujima, Hiroko Yamada, Hiroko Yamada, Takahiro Nakae, Hidemitsu Uno, Organic and Biomolecular Chemistry, 12, (8) 1309 - 1317,   2014年02月28日, Bicyclo[2.2.2]octadiene-fused (BCOD-fused) bis(benzoborondipyrromethene)s (bisbenzoBODIPYs) bearing electron-withdrawing groups such as fluorine and cyano groups were prepared either by incorporating tetrafluoroisoindole moieties into BODIPY chromophores or by introducing cyano or ethoxycarbonyl groups at the 3,5-positions. The BCOD-fused bisbenzoBODIPYs were quantitatively converted to the corresponding benzene-fused bisbenzoBODIPYs by a retro-Diels-Alder reaction. The π-fused bisbenzoBODIPYs were found to have intense absorption in the near-infrared region and not to have any strong absorption bands in the visible region. Moreover, the bisbenzoBODIPYs were stable under atmospheric conditions. © 2014 The Royal Society of Chemistry.
  • Synthesis and properties of 6-methoxy- and 6-dimethylamino-1-methylthio- and 1,3-bis(methylthio)azulenes and triflic anhydride-mediated synthesis of their biaryl derivatives
    Taku Shoji, Akifumi Maruyama, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima, Junya Higashi, Kozo Toyota, Noboru Morita, Bulletin of the Chemical Society of Japan, 87, (1) 141 - 154,   2014年01月28日, 6-Methoxy- and 6-dimethylaminoazulenes with methylthio groups at the 1- or 1,3-positions have been prepared by electrophilic substitution of the corresponding azulenes with DMSO in the presence of acid anhydride, followed by treatment with Et 3 N. The products, 1-methylthioazulenes, reacted with Tf 2 O to afford the corresponding 1,1′-biazulene derivatives in moderate yields. The redox behavior of these azulene and 1,1′-biazulene derivatives was examined by cyclic voltammetry (CV), which revealed reversible electron transfers under electrochemical oxidation conditions. 6-Dimethylamino-1,3-bis(methylthio)azulenes with a heteroaiyl group at the 2-position were also prepared by the reaction of 6-dimethylamino-1,3- bis(methylthio)azulene with triflates of iV-containing heterocycles, i.e., pyridine, quinoline, isoquinoline, acridine, and 1,10-phenanthroline, followed by treatment with KOH in alcohols. © 2013 The Chemical Society of Japan.
  • Synthesis of 2-aryl- and 6-heteroaryl-1,3-di(4-pyridyl)azulenes by Katritzky's pyridylation of 2-aryl-and 6-heteroarylazulenes
    Taku Shoji, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Masafumi Yasunami, Junya Higashi, Noboru Morita, Heterocycles, 89, (11) 2588 - 2603,   2014年01月01日, © 2014 The Japan Institute of Heterocyclic Chemistry. Preparation of 2-aryl- and 6-heteroarylazulenes 2-6 and 8-10 was established by the palladium-catalyzed cross-coupling reaction of the corresponding haloazulenes with lithium aryl- and heteroarylmagnesium ate complexes, which were readily prepared from the corresponding aryl and heteroaryl halides. The reaction of 2-6 and 8-10, except for 3 and 8, with pyridine in the presence of Tf 2 O, followed by treatment with KOH in MeOH afforded the corresponding 2-aryl- and 6-heteroaryl-1,3-di(4-pyridyl)azulenes 11-16 in good yields.
  • Synthesis of 2,2'-diamino-1,1'-biazulenes by the copper-catalyzed homocoupling reaction of 2-aminoazulenes
    Taku Shoji, Taku Shoji, Akifumi Maruyama, Atsuyo Yamamoto, Yuki Fujiwara, Shunji Ito, Tetsuo Okujima, Noboru Morita, Chemistry Letters, 43, (7) 1122 - 1124,   2014年01月01日, Synthesis of 2,2'-diamino-1,1'-biazulene derivatives 5 and 911 was established by copper-catalyzed homocoupling reaction of the corresponding 2-aminoazulenes 3 and 68. The palladium-catalyzed cross-coupling reactions of 6,6'-dibromo- 1,1'-biazulene derivative 9 were also established under the SuzukiMiyaura and SonogashiraHagihara conditions. © 2014 The Chemical Society of Japan.
  • Synthesis of NIR-emitting O-chelated BODIPYs fused with benzene and acenaphthylene
    Tetsuo Okujima, Yoichi Shida, Keishi Ohara, Yuya Tomimori, Motoyoshi Nishioka, Shigeki Mori, Takahiro Nakae, Takahiro Nakae, Hidemitsu Uno, Journal of Porphyrins and Phthalocyanines, 18, (8/9) 752 - 761,   2014年01月01日, Copyright © 2014 World Scientific Publishing Company. A series of O-chelated BODIPYs fused with aromatic rings such as benzene and acenaphthylene at β,β-positions was synthesized as a near-infrared dye. The photophysical properties were examined by UV-vis-NIR absorption and fuorescence measurement. Acenaphthylene-fused O-BODIPYs showed a intense absorption at 750-840 nm with the ε of 10 5 M -1 .cm -1 . and a fuorescene emission at 770-850 nm with the high Φ value of 0.06-0.43.
  • Bisarylation of 1,1′,3,3′-tetrahalo-2,2′-biazulene under suzukimiyaura cross-coupling conditions
    Takahiro Nakae, Takashi Kikuchi, Shigeki Mori, Tetsuo Okujima, Toshihiro Murafuji, Hidemitsu Uno, Chemistry Letters, 43, (4) 504 - 506,   2014年01月01日, 1,3-Bisarylated-2,2′-biazulene 1 and 1,1′-bisarylated-2, 2′-biazulene 1′ were obtained by the SuzukiMiyaura crosscoupling reaction of 1,1′,3,3′-tetrahalo-2,2′-biazulene 2 with 4-tert-butylphenylboronic acid (3b). The other two halogen atoms were reductively removed by hydrogenation under the same reaction conditions. The major regioisomer 1 was obtained with a selectivity of up to 94% (15:1) and a combined yield of 1 and 1′ of up to 77%. © 2014 The Chemical Society of Japan.
  • Synthesis and molecular structure of cyclo[8](9,10-dihydro-9,10-anthraceno)pyrrole
    Tetsuo Okujima, Chie Ando, Shigeki Mori, Takahiro Nakae, Hiroko Yamada, Hidemitsu Uno, Heterocycles, 88, (1) 417 - 424,   2014年01月01日, © 2014 The Japan Institute of Heterocyclic Chemistry. Cyclo[8]pyrrole with eight 9,10-dihydroanthracene wings was synthesized by oxidative coupling of the corresponding 2,2′-bipyrrole in good yield. The molecular structure was determined by single crystal X-ray analysis. The three-dimensionally structured cyclo[8] pyrrole possessed a cavity created by a pair of slip-stacked cyclo[8]pyrroles.
  • Synthesis of 1,3-Bis(tetracyano-2-azulenyl-3-butadienyl)azulenes by the [2+2] Cycloaddition-Retroelectrocyclization of 1,3-Bis(azulenylethynyl)azulenes with Tetracyanoethylene
    Taku Shoji, Taku Shoji, Mitsuhisa Maruyama, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Chemistry - A European Journal, 20, (37) 11903 - 11912,   2014年01月01日, 1,3-Bis(azulenylethynyl)azulene derivatives 9-14 have been prepared by palladium-catalyzed alkynylation of 1-ethynylazulene 8 with 1,3-diiodoazulene 1 or 1,3-diethynylazulene 2 with the corresponding haloazulenes 3-7 under Sonogashira-Hagihara conditions. Bis(alkynes) 9-14 reacted with tetracyanoethylene (TCNE) in a formal [2+2] cycloaddition- retroelectrocyclization reaction to afford the corresponding new bis(tetracyanobutadiene)s (bis(TCBDs)) 15-20 in excellent yields. The redox behavior of bis(TCBD)s 15-20 was examined by using CV and differential pulse voltammetry (DPV), which revealed their reversible multistage reduction properties under the electrochemical conditions. Moreover, a significant color change of alkynes 9-14 and TCBDs 15-20 was observed by visible spectroscopy under the electrochemical reduction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Study on Hinsberg thiophene synthesis of 4,8-dihydro-4,8-ethanobenzo[1,2-c;4,5-c′]dithiophene
    Kazunari Tagawa, Shigeki Mori, Takahiro Nakae, Tetsuo Okujima, Hidemitsu Uno, Heterocycles, 88, (1) 453 - 462,   2014年01月01日, © 2014 The Japan Institute of Heterocyclic Chemistry. The Hinsberg thiophene synthesis using 4,5,6,7-tetrahydro-4,7-ethanothiophene-5,6-dione and diethyl thiodiglycolate afforded a mixture of diethyl 4,8-dihydro-4,8-ethanobenzo[1,2-c;4,5-c′]dithiophene-1,3-dicarboxylate and its dihydrate, although the yields were low. The latter dihydrate was converted to the former dithiophene in a good yield by the treatment with Ac 2 O and DMAP.
  • Solution-processed anthradithiophene-PCBM p-n junction photovoltaic cells fabricated by using the photoprecursor method
    Hiroko Yamada, Hiroko Yamada, Yuji Yamaguchi, Ryuta Katoh, Takao Motoyama, Tatsuya Aotake, Daiki Kuzuhara, Mitsuharu Suzuki, Tetsuo Okujima, Hidemitsu Uno, Naoki Aratani, Ken Ichi Nakayama, Ken Ichi Nakayama, Chemical Communications, 49, (99) 11638 - 11640,   2013年12月25日, P-n junction solar cells based on anthradithiophene (ADT) as a p-type semiconductor were fabricated by using the photoprecursor method in which an α-diketone-type precursor was spin-coated and then transformed to ADT in situ by photoirradiation. Combination with PC 71 BM as an n-layer material led to 1.54% photoconversion efficiency. © 2013 The Royal Society of Chemistry.
  • Synthesis, properties, and redox behavior of tetracyanobutadiene and dicyanoquinodimethane chromophores bearing two azulenyl substituents
    Taku Shoji, Mitsuhisa Maruyama, Erika Shimomura, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Noboru Morita, Journal of Organic Chemistry, 78, (24) 12513 - 12524,   2013年12月20日, Acetylene derivatives with an azulenyl group at both terminals have been prepared by palladium-catalyzed alkynylation under Sonogashira-Hagihara conditions. These alkynes reacted with tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane in a formal [2 + 2] cycloaddition- retroelectrocyclization reaction to afford the corresponding new tetracyanobutadienes (TCBDs) and dicyanoquinodimethanes (DCNQs), respectively, in excellent yields. Intramolecular CT absorption bands were found in the UV-vis spectra of the novel chromophores, and CV and DPV showed that they exhibited a reversible two-stage reduction wave, due to the electrochemical reduction of TCBD and DCNQ moieties. Color changes were also observed during the electrochemical reduction. © 2013 American Chemical Society.
  • Synthesis and properties of azulene-substituted donor-acceptor chromophores connected by arylamine cores
    Taku Shoji, Erika Shimomura, Mitsuhisa Maruyama, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Noboru Morita, European Journal of Organic Chemistry, 2013, (34) 7785 - 7799,   2013年12月01日, 1-Ethynylazulenes connected by several arylamine cores reacted with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2+2] cycloaddition-cycloreversion reaction to afford the corresponding tetracyanobutadiene (TCBD) and dicyanoquinodimethane (DCNQ) chromophores, respectively, in excellent yields. The intramolecular charge-transfer (ICT) characters between the donor (azulene and arylamine cores) and acceptor (TCBD and DCNQ units) moieties were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the new TCBD and DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions. 1-Ethynylazulenes connected by several types of arylamine cores reacted with TCNE and TCNQ in formal [2+2] cycloadditions to afford corresponding tetracyanobutadiene and dicyanoquinodimethane chromophores, respectively. Cyclic voltammetry of the chromophores revealed their multistep reduction properties; significant color changes were also visible during electrochemical reduction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Synthesis and properties of boron complexes of [14]triphyrins(2.1.1)
    Daiki Kuzuhara, Zhaoli Xue, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno, Naoki Aratani, Hiroko Yamada, Hiroko Yamada, Chemical Communications, 49, (79) 8955 - 8957,   2013年10月11日, Boron complexes of [14]triphyrins(2.1.1) were prepared from free-base [14] triphyrins(2.1.1) with phenylboron dichloride. The absorption spectrum of the meso-free β-alkyl-triphyrin boron complex in CH 2 Cl 2 showed a broad weak band at around 640 nm assigned to transition from B-phenyl to the triphyrin, while that of the meso-aryl benzotriphyrin boron complex showed only Soret and Q bands. © 2013 The Royal Society of Chemistry.
  • Acenaphthylene-fused cyclo[8]pyrroles with intense near-IR-region absorption bands
    Tetsuo Okujima, Chie Ando, John Mack, John Mack, Shigeki Mori, Ichiro Hisaki, Takahiro Nakae, Hiroko Yamada, Keishi Ohara, Nagao Kobayashi, Hidemitsu Uno, Chemistry - A European Journal, 19, (41) 13970 - 13978,   2013年10月04日, An acenaphthylene-fused cyclo[8]pyrrole was synthesized by using an oxidative coupling reaction of the corresponding 2,2'-bipyrrole. Two conformational isomers 1 a and 1 b were isolated, and their molecular structures were eluc idated by X-ray crystallographic studies. The less-polar and lower-symmetry 1 b isomer can be converted into the 1 a isomer through a thermal ring flip. Application of the perimeter model developed by Michl to magnetic circular dichroism spectroscopic data and theoretical calculations demonstrate that there is a marked redshift of the near-IR absorption maxima relative to cyclo[8] isoindole because there is a significant stabilization of the LUMO due to the differing effects of a fused ring expansion with acenaphthylene and benzene moieties on the frontier π molecular orbitals. Fused ring expansion: An oxidative coupling reaction of the corresponding 2,2'-bipyrrole leads to the synthesis of an acenaphthylene-fused cyclo[8]pyrrole. Application of Michl's perimeter model to magnetic circular dichroism spectral data and the results of theoretical calculations demonstrate that there is a marked redshift of the near-IR absorption maxima (see figure). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • MCD spectroscopy and TD-DFT calculations of low-symmetry acenaphthoporphyrins with dual fluorescence
    John Mack, John Mack, Jun Nakamura, Tetsuo Okujima, Hiroko Yamada, Hidemitsu Uno, Nagao Kobayashi, Journal of Porphyrins and Phthalocyanines, 17, (10) 996 - 1007,   2013年10月01日, Magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations are used to analyze the electronic structure and optical properties of low-symmetry acenaphthoporphyrins with AAAB, ABAB and AABB structures. Evidence for dual fluorescence caused by tautomerism has been identified in the emission spectra of the AAAB and ABAB compounds. The sign sequences observed for the Q and B bands in the MCD spectra have been used to validate the results of the TD-DFT calculations. An anomalous +/- sign sequence is observed in the B band region with ascending energy similar to that reported previously for metal tetraphenyltetraacenaphthoporphyrin complexes. Copyright © 2013 World Scientific Publishing Company.
  • A soluble bispentacenequinone precursor for creation of directly 6,6′-linked bispentacenes and a tetracyanobipentacenequinodimethane
    Kazuki Tanaka, Naoki Aratani, Naoki Aratani, Daiki Kuzuhara, Sadaaki Sakamoto, Tetsuo Okujima, Noboru Ono, Hidemitsu Uno, Hiroko Yamada, Hiroko Yamada, RSC Advances, 3, (35) 15310 - 15315,   2013年09月21日, We have synthesized 13,13′-(3,5-bis(trifluoromethyl)phenyl)-6, 6′-bipentacene from a soluble bispentacenequinone precursor. Bispentacene takes orthogonal conformation in the solid state and exhibits four reversible redox potentials. In addition, a tetracyanobipentacenequinodimethane was obtained for the first time from the pure bispentacenequinone. © The Royal Society of Chemistry 2013.
  • Effect of the orthoquinone moiety in 9,10-phenanthrenequinone on its ability to induce apoptosis in HCT-116 and HL-60 cells
    Noriyuki Hatae, Jun Nakamura, Tetsuo Okujima, Minoru Ishikura, Takumi Abe, Satoshi Hibino, Tominari Choshi, Chiaki Okada, Hiroko Yamada, Hidemitsu Uno, Eiko Toyota, Bioorganic and Medicinal Chemistry Letters, 23, (16) 4637 - 4640,   2013年08月15日, 9,10-Phenanthrenequinone (9,10-PQ) is one of the most abundant quinones among diesel exhaust particulates. Recent data have suggested that quinones induce apoptosis in immune, epithelial and tumor cells, leading to respirator illness; however, the mechanisms by which quinones induce apoptosis and the structure required for this remain unknown. We studied the antitumor activity of 9,10-PQ analogs against two human tumor cell lines, HCT-116 colon tumor cells and HL-60 promyelocytic leukemia cells. The loss of the cis-orthoquinone unit in 9,10-PQ abrogated its ability to induce apoptosis in the two tumor cell lines, and the LC 50 values of these analogs were indicated over 10 μM. An analog of 9,10-PQ in which the biaryl unit had been deleted displayed a reduced ability to induce tum or cell apoptosis, while the analogs 1,10-phenanthroline- 5,6-dione (9) and pyrene-4,5-dione (10), which also had modified biaryl units, exhibited increased tumor cell apoptotic activity. The cis-orthoquinone unit in 9,10-PQ was identified as essential for its ability to induce apoptosis in tumor cells, and its biaryl unit is also considered to influence orthoquinone- mediated apoptotic activity. © 2013 Elsevier Ltd. All rights reserved.
  • η5-cyclopentadienyliron(II)-[14]triphyrin(2.1.1) sandwich compounds: Synthesis, characterization, and stable redox interconversion
    Zhaoli Xue, Zhaoli Xue, Daiki Kuzuhara, Shinya Ikeda, Yuka Sakakibara, Kei Ohkubo, Naoki Aratani, Naoki Aratani, Tetsuo Okujima, Hidemitsu Uno, Shunichi Fukuzumi, Shunichi Fukuzumi, Hiroko Yamada, Hiroko Yamada, Angewandte Chemie - International Edition, 52, (28) 7306 - 7309,   2013年07月08日, A semiferrocene complex with a [14]triphyrin(2.1.1) (TriP) ligand has been synthesized. The structure and properties are characterized by X-ray crystallographic analysis, UV/Vis spectroscopy, and variable-temperature 1 H NMR spectroscopy. The Fe II and Fe III complexes are electrochemically reversible. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Synthesis of 1,6′-Bi- and 1,6′:3,6″-terazulenes from 1-pyridyl- and 1,3-Di(pyridyl)azulenes by the Ziegler-Hafner method
    Taku Shoji, Atsuyo Yamamoto, Erika Shimomura, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Noboru Morita, Chemistry Letters, 42, (6) 638 - 640,   2013年06月12日, The synthesis of 1,6′-biazulenes 3a and 3b and 1,6′:3,6″- terazulenes 7a and 7b was established by one-pot reactions via the Zincke-type ring-opening of the corresponding pyridinium salts with diethylamine, followed by the reaction with cyclopentadiene in the presence of sodium methoxide. The intramolecular charge-transfer characters between azulene rings were investigated by UVvis spectroscopy and theoretical calculations. © 2013 The Chemical Society of Japan.
  • In situ preparation of highly fluorescent pyrene-dyes from non-luminous precursors upon photoirradiation
    Tatsuya Aotake, Hiroshi Tanimoto, Hidekatsu Hotta, Daiki Kuzuhara, Tetsuo Okujima, Hidemitsu Uno, Hiroko Yamada, Hiroko Yamada, Chemical Communications, 49, (35) 3661 - 3663,   2013年05月07日, The non-luminous precursor, 2-(1-pyrenyl)-9,10-dihydro-9,10- ethanoanthracene-11,12-dione, was photochemically converted to highly-fluorescent 2-(1-pyrenyl)anthracene quantitatively in solution and in the PMMA film and the fluorescence quantum yield of the acene in benzonitrile was as high as 0.99. © The Royal Society of Chemistry 2013.
  • Synthesis of 2-azulenyl-1,1,4,4-tetracyano-3-ferrocenyl-1,3-butadienes by [2+2] cycloaddition of (Ferrocenylethynyl)azulenes with tetracyanoethylene
    Taku Shoji, Shunji Ito, Tetsuo Okujima, Noboru Morita, Chemistry - A European Journal, 19, (18) 5721 - 5730,   2013年04月26日, 1-, 2-, and 6-(Ferrocenylethynyl)azulene derivatives 10-16 have been prepared by palladium-catalyzed alkynylation of ethynylferrocene with the corresponding haloazulenes under Sonogashira-Hagihara conditions. Compounds 10-16 reacted with tetracyanoethylene (TCNE) in a [2+2] cycloaddition- cycloreversion reaction to afford the corresponding 2-azulenyl-1,1,4,4,- tetracyano-3-ferrocenyl-1,3-butadiene chromophores 17-23 in excellent yields. The redox behavior of the novel azulene chromophores 17-23 was examined by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions. Colorful chemistry: 1-, 2-, and 6-(ferrocenylethynyl)azulenes have been prepared by Sonogashira-Hagihara reaction of ethynylferrocene with the corresponding haloazulenes (see scheme). These ethynylazulene derivatives react with tetracyanoethylene in a [2+2] cycloaddition-cycloreversion reaction to afford the corresponding azulene chromophores in excellent yields. Significant color change of the novel 1,1,4,4-tetracyano-1,3-butadiene (TCBD) derivatives was observed by visible spectroscopy under electrochemical reduction conditions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Photochemical synthesis of naphthacene and its derivatives for irreversible photo-responsive fluorescent molecules
    Tatsuya Aotake, Yuko Yamashita, Tetsuo Okujima, Nobuhiko Shirasawa, Yukari Jo, Shigeo Fujimori, Hidemitsu Uno, Noboru Ono, Hiroko Yamada, Hiroko Yamada, Tetrahedron Letters, 54, (14) 1790 - 1793,   2013年04月03日, Highly fluorescent naphthacene derivatives and their photoconvertible precursors were synthesized for irreversibly photo-responsive fluorescent molecules. The fluorescence quantum yields (Φ f ) of the precursors were less than 0.02, and the precursors can be converted to the highly fluorescent naphthacene derivatives (Φ f = 0.67-0.70) quantitatively by photo-irradiation. © 2013 Elsevier Ltd. All rights reserved.
  • Thiatriphyrin(2.1.1): A core-modified contracted porphyrin
    Daiki Kuzuhara, Yuka Sakakibara, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno, Hiroko Yamada, Hiroko Yamada, Angewandte Chemie - International Edition, 52, (12) 3360 - 3363,   2013年03月18日, Elusive in its free-base form, the core-modified contracted porphyrin thiatriphyrin(2.1.1) was prepared with p-tolyl substituents by intramolecular McMurry coupling and then converted into various alkoxy-substituted analogues (see scheme; DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). In the presence of trifluoroacetic acid (TFA), each of these compounds was transformed into the protonated thiatriphyrin(2.1.1), which exhibited moderate aromaticity. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Synthesis, structure and properties of ethyl naphth[2,3-f]isoindole-1- carboxylate
    Aya Seike, Kaoru Yamagami, Yoshimasa Kakitani, Miki Kuwajima, Hiroki Uoyama, Shin Ichi Nagaoka, Takahiro Nakae, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno, RSC Advances, 3, (9) 3006 - 3016,   2013年03月05日, Ethyl 12-oxo-4,11-dihydro-4,11-ethanonaphth[2,3-f]isoindole-1-carboxylate (2) was prepared from 7-tert-butoxynorbornadiene and quantitatively converted to ethyl naphth[2,3-f] isoindole-1-carboxylate (3) by the thermal or photochemical cheletropic reaction. Ethyl naphth[2,3-f]isoindole-1-carboxylate (3) existed in a 2H-form both in solution and as a solid, and gradually dimerized to give a dianthradiazafulvalene derivative under aerobic conditions. © 2013 The Royal Society of Chemistry.
  • Synthesis and characterization of new platinum(II) and platinum(IV) triphyrin complexes
    Zhaoli Xue, Zhaoli Xue, Daiki Kuzuhara, Shinya Ikeda, Tetsuo Okujima, Shigeki Mori, Hidemitsu Uno, Hiroko Yamada, Hiroko Yamada, Inorganic Chemistry, 52, (4) 1688 - 1690,   2013年02月18日, Metalation of 6,13,20,21-tetrakis(4-methylphenyl)-22H-tribenzo[14] triphyrin(2.1.1) with PtCl 2 gave a platinum(II) complex having a square-planar coordination structure with two pyrrolic nitrogen atoms and two chloride ions, with a saddle-shaped macrocycle. This platinum(II) complex was easily oxidized by air to an octahedral platinum(IV) complex coordinated by three pyrrolic nitrogen atoms as a tridentate monoanionic cyclic ligand and three chloride ions. When platinum(II) triphyrin was crystallized in air, an oxygen atom was incorporated between two α-carbon atoms of the pyrroles as an oxygen bridge to intercept the 14π aromatic system. © 2013 American Chemical Society.
  • Synthesis, properties and redox behavior of ene-diyne scaffolds bearing 1- and 2-azulenyl groups at the periphery
    Taku Shoji, Erika Shimomura, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima, Noboru Morita, European Journal of Organic Chemistry, 2013, (5) 957 - 964,   2013年02月01日, Ene-diyne systems possessing 1- and 2-azulenyl groups at the periphery were prepared by palladium-catalyzed cross-coupling reaction of 1- and 2-ethynylazulenes with 9-dibromomethylene-9H-fluorene and 9,10- bis(dibromomethylene)-9,10-dihydroanthracene or 2-iodoazulene with 9,10-bis(diethynylmethylene)-9,10-dihydroanthracene under Sonogashira-Hagihara conditions. The redox behavior of the ene-diyne compounds was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Moreover, a significant color change of the ene-diyne derivatives was observed with visible spectroscopy under electrochemical reduction conditions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Synthesis of bis-naphthoporphyrins
    Hiroki Uoyama, Hiroko Yamada, Tetsuo Okujima, Hidemitsu Uno, Heterocycles, 86, (1) 515 - 534,   2012年12月01日, Ethanonaphthoporphyrins with a halogen atom at the position were prepared by the [3+1] porphyrin synthesis of halogen-substituted ethanobenz[f] isoindole with a tripyrrane derivative. The halogeno porphyrins were converted to the corresponding ethynyl and pinacolatoboronyl compounds by Sonogashira and borylation reactions, respectively. Suzuki, Sonogashira, and Glaser coupling reactions of these ethanonaphthoporphyrins gave bis-porphyrins connected with no atom, acetylene, and butadiyne, respectively. Retro Diels-Alder reaction of these bis-porphyrins brought about the conversion of bicyclo[2.2.2]octadiene (BCOD) to benzene moieties to give bis-naphthoporphyrins, quantitatively. © 2012 The Japan Institute of Heterocyclic Chemistry.
  • Synthesis and properties of azulene-substituted thiophenes, terthiophenes and dithienothiophenes
    Tetsuo Okujima, Akiko Toda, Yoko Miyashita, Ayumi Nonoshita, Hiroko Yamada, Noboru Ono, Hidemitsu Uno, Heterocycles, 86, (1) 637 - 648,   2012年12月01日, Bis(azulenylethynyl)thiophenes, terthiophenes, and dithienothiophenes have been synthesized by the Pd-catalyzed cross-coupling of the corresponding diiodothiophenes with 1- and 6-ethynylazulenes under Sonogashira-Hagihara conditions. © 2012 The Japan Institute of Heterocyclic Chemistry.
  • FET performance and substitution effect on 2,6-dithienylanthracene devices prepared by photoirradiation of their diketone precursors
    Hiroko Yamada, Hiroko Yamada, Chika Ohashi, Tatsuya Aotake, Shuhei Katsuta, Yoshihito Honsho, Hiroo Kawano, Tetsuo Okujima, Hidemitsu Uno, Noboru Ono, Shu Seki, Ken Ichi Nakayama, Ken Ichi Nakayama, Chemical Communications, 48, (90) 11136 - 11138,   2012年11月21日, Hole mobility was evaluated by top-contact bottom gate field effect transistor and time resolved microwave conductivity measurements in 2,6-dithienylanthracene and hexyl-substituted 2,6-dithienylanthracene films prepared by spin-coating of their α-diketone precursors followed by photoirradiation, revealing enough high potentials for semiconducting films with charge carrier mobilities of 0.8-0.9 cm 2 V -1 s -1 in the photo-irradiated films. © 2012 The Royal Society of Chemistry.
  • Synthesis of push-pull chromophores by the sequential [2 + 2] cycloaddition of 1-azulenylbutadiynes with tetracyanoethylene and tetrathiafulvalene
    Taku Shoji, Shunji Ito, Tetsuo Okujima, Noboru Morita, Organic and Biomolecular Chemistry, 10, (41) 8308 - 8313,   2012年11月07日, Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor-acceptor chromophores and novel azulene-substituted 6,6-dicyanofulvene derivatives. © The Royal Society of Chemistry 2012.
  • Retro-Diels-Alder approach to the synthesis of π-expanded azuliporphyrins and their porphyrinoid aromaticity
    Tetsuo Okujima, Tasuku Kikkawa, Haruyuki Nakano, Hiroshi Kubota, Nobumasa Fukugami, Noboru Ono, Hiroko Yamada, Hidemitsu Uno, Chemistry - A European Journal, 18, (40) 12854 - 12863,   2012年10月01日, Bicyclo[2.2.2]octadiene (BCOD) fused azuliporphyrins were synthesized by 3+1 porphyrin synthesis of azulitripyrranes with diformylpyrroles. Subsequent retro-Diels-Alder reaction of the BCOD-fused azuliporphyrins afforded azulibenzo-, azulidibenzo-, and azulitribenzoporphyrins 1-5. NMR and UV/Vis spectra, as well as nucleus-independent chemical shift (NICS) calculations revealed that 1-5 and their diprotonated dications exhibit relatively low porphyrinoid aromaticity, which was dependent on the position and number of fused benzene rings present. Porphyrins: A series of azulibenzoporphyrins were synthesized based on 3+1 porphyrin synthesis and retro-Diels-Alder reaction of bicyclo[2.2.2] octadiene-fused precursors (see scheme). UV/Vis spectra and NICS calculations revealed that their diprotonated dications exhibited a low porphyrinoid aromaticity from the porphyrinlike π circuit, which was dependent on the position and number of fused benzene rings. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • π-Fused bis-BODIPY as a candidate for NIR dyes
    Mitsunori Nakamura, Hiroyuki Tahara, Kohtaro Takahashi, Toshi Nagata, Hiroki Uoyama, Daiki Kuzuhara, Shigeki Mori, Tetsuo Okujima, Hiroko Yamada, Hidemitsu Uno, Organic and Biomolecular Chemistry, 10, (34) 6840 - 6849,   2012年09月14日, Benzene-fused bis-(borondipyrromethene)s (bis-BODIPYs) were synthesized by retro-Diels-Alder reaction of the corresponding bicyclo[2.2.2] octadiene-fused (BCOD-fused) bis-BODIPYs, which were, in turn, prepared from 4,8-ethano-4,8-dihydropyrrolo[3,4-f] isoindole derivatives. The π-fused bis-BODIPY chromophores were designed to show intensive absorption and strong fluorescence in the near-infrared region and not to have any strong absorption in the visible region. A 6,10-dibora-5a,6a,9a,10a-tetraaza-s-indaceno[2,3-b:6,5- b′]difluorene derivative (syn-bis-benzoBODIPY) obtained by a thermal retro-Diels-Alder reaction of the corresponding BCOD-fused BODIPY dimer has strong absorption and emission bands at 775 and 781 nm, respectively. The absolute quantum yield is 0.36. The absorption is more than 5.0 times stronger than other absorptions observed in the visible region. In the case of 6,15-dibora-5a,6a,14a,15a-tetraaza-s-indaceno[2,3-b:6,7-b′] difluorene derivatives (anti-bis-benzoBODIPY), the absorption and emission maxima exceed 840 nm. © 2012 The Royal Society of Chemistry.
  • Synthesis of Pyrroles and Their Derivatives from Isocyanides
    Noboru Ono, Tetsuo Okujima, Isocyanide Chemistry: Applications in Synthesis and Material Science,   2012年08月23日
  • Synthesis and spectroscopic properties of ring-fused thiophene bridged push-pull dyes and their application in dye-sensitized solar cells
    Quan Liu, Fan Tai Kong, Tetsuo Okujima, Hiroko Yamada, Hiroko Yamada, Song Yuan Dai, Hidemitsu Uno, Noboru Ono, Xiao Zeng You, Zhen Shen, Tetrahedron Letters, 53, (26) 3264 - 3267,   2012年06月27日, Bisdimethylfluorenylamino-based push-pull dyes bearing one or two benzo[c]thiophene and its precursor bicyclo[2.2.2] octadiene (BCOD) fused thiophene as π bridge have been synthesized. The effect of fused-ring on thiophene bridge for the spectroscopic and electrochemical properties of these dyes has been investigated. Dye-sensitized solar cells fabricated with these dyes show moderate photovoltaic properties. © 2012 Elsevier Ltd. All rights reserved.
  • Effective synthesis of diiodinated picene and dibenzo[a,h]anthracene by AuCl-catalyzed double cyclization
    Takahiro Nakae, Ryuji Ohnishi, Yoshiharu Kitahata, Tatsuya Soukawa, Hisako Sato, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno, Hiroshi Sakaguchi, Tetrahedron Letters, 53, (13) 1617 - 1619,   2012年03月28日, 6,13-Diiododibenzo[a,h]anthracene and 5,8-diiodopicene were synthesized by AuCl-catalyzed double cyclization. The highly selective reaction yielded a new class of peri-halogenated fused aromatics. © 2011 Elsevier Ltd. All rights reserved.
  • Synthesis of donor-acceptor chromophores by the [2 + 2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane
    Taku Shoji, Junya Higashi, Shunji Ito, Tetsuo Okujima, Masafumi Yasunami, Noboru Morita, Organic and Biomolecular Chemistry, 10, (12) 2431 - 2438,   2012年03月28日, Arylethynyl-2H-cyclohepta[b]furan-2-ones reacted with 7,7,8,8- tetracyanoquinodimethane (TCNQ) in a formal [2 + 2] cycloaddition reaction, followed by ring opening of the initially formed cyclobutene derivatives, to afford the corresponding dicyanoquinodimethane (DCNQ) chromophores in excellent yields. The intramolecular charge-transfer (ICT) interactions between the 2H-cyclohepta[b]fura n-2-one ring and DCNQ acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties depended on the number of DCNQ units in the molecule. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions. © The Royal Society of Chemistry 2012.
  • Synthesis, structure, and photochemistry of 5,14-diketopentacene
    Tatsuya Aotake, Shinya Ikeda, Daiki Kuzuhara, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno, Hiroko Yamada, Hiroko Yamada, European Journal of Organic Chemistry, 2012, (9) 1723 - 1729,   2012年03月01日, 5,14-α-Diketopentacene, a structural isomer of 6,13-α- diketopentacene, was prepared from pentacene in three steps. In addition to the typical n-π* absorption of the diketone moiety at around 468 nm and the anthracene-like absorption at 333, 349, and 367 nm, a broad absorption was observed at around 386 nm, which could be assigned to an intramolecular charge-transfer absorption from anthracene to the diketone moiety. 5,14-α-Diketopentacene could be converted into pentacene quantitatively by photoirradiation at 405 and 468 nm in toluene with quantum yields of 2.3 and 2.4%, respectively, and these values are higher than the quantum yield of 1.4% obtained for 6,13-α-diketopentacene irradiated at 468 nm. The quantum yields in acetonitrile were lowered to 0.33 and 0.28% with irradiation at 405 and 468 nm. The crystal structure of 5,14-α-diketopentacene showed a CH-π interaction and π-π stacking between neighbouring anthracene and benzene moieties. The lower solubility of 5,14-α-diketopentacene compared with the 6,13-isomer could be explained by this crystal structure. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • First synthesis of 2-heteroarylazulenes by the electrophilic substitution of azulene with triflate of N-containing heterocycles
    Taku Shoji, Yuta Inoue, Shunji Ito, Tetsuo Okujima, Noboru Morita, Heterocycles, 85, (1) 35 - 41,   2012年01月09日, An efficient synthesis of 2-heteroarylazulene derivatives was established via electrophilic substitution. The reaction of 6-dimethylamino-1,3- di(methylthio)azulene (1a) with the triflate of N-containing heteroarenes proceeded in the presence of excess heteroarenes to afford the corresponding 2-dihydroheteroarylazulene derivatives 3-7. The 2-dihydroheteroarylazulene derivatives were readily converted into the desired 2-heteroarylazulene derivatives 8-11 by the treatment with KOH in alcohols in excellent yields, except for 4 and 5. © 2012 The Japan Institute of Heterocyclic Chemistry.
  • Synthesis of pentacene-, tetracene- and anthracene bisimides using double-cyclization reaction mediated by bismuth(iii) triflate
    Shuhei Katsuta, Kazuki Tanaka, Yukihiro Maruya, Shigeki Mori, Sadahiro Masuo, Sadahiro Masuo, Tetsuo Okujima, Hidemitsu Uno, Ken Ichi Nakayama, Ken Ichi Nakayama, Hiroko Yamada, Hiroko Yamada, Chemical Communications, 47, (36) 10112 - 10114,   2011年09月28日, Novel bisimide-fused acenes were synthesized via bismuth triflate mediated double-cyclization reaction of acid chlorides and isocyanates. Their optical and electrical properties revealed significantly smaller HOMO-LUMO gaps compared with those of their parent acenes. Fabricated OFET based on tetracene bisimide showed n-type OFET outputs. © The Royal Society of Chemistry 2011.
  • Porphyrin molecular tweezers for fullerenes
    Hidemitsu Uno, Mina Furukawa, Akiko Fujimoto, Hiroki Uoyama, Hajime Watanabe, Tetsuo Okujima, Hiroko Yamada, Shigeki Mori, Makoto Kuramoto, Tatsunori Iwamura, Noriyuki Hatae, Fumito Tani, Naoki Komatsu, Journal of Porphyrins and Phthalocyanines, 15, (9/10) 951 - 963,   2011年09月01日, Facing zinc bisporphyrins connected with diethanoanthracene and diethanonaphthacene (syn-1 and syn-2) are prepared by double [3+1] porphyrin synthesis of tripyrranedicarbaldehyde with syn-5,11-dimethoxy-4,6,10,12- tetrahydro-4,12;6,10-diethanoanthracene[2,3-c;7,8-c′] dipyrrole and syn-4,7,11,14- tetrahydro-4,14;7,11-diethanonaphthacene[2,3-c;8,9-c′] dipyrrole. These bisporphyrins contain large clefts with different sizes capable for complexation with fullerenes such as C 60 and C 70 . These designed syn-oriented bisporphyrins serve as effective and selective molecular tweezers for C 70 . Binding affinity of the zinc bisporphyrins, namely, syn-1 and syn-2, towards C 60 and C 70 in solution is determined by employing UV-vis spectrophotometric technique. Values of binding constants (K) in toluene for the non-covalent complexes of syn-1 with C 60 and C 70 are estimated to be 3.1(4) × 10 4 and 5.0(2) × 10 5 M -1 , respectively, and those of syn-2 with C 60 and C 70 are enumerated to be 2.1(4) × 10 4 and 1.70(13) × 10 5 M -1 , respectively. Binding of C 60 and C 70 in the clefts of syn-1 and syn-2 is clearly demonstrated by the crystal structures of C 60 /syn-1, C 70 /syn-1, C 60 /syn-2, and C 70 /syn-2 complexes. In the crystal structures with C 70 , the directions of the long axis of C 70 are found to be quite different: in the case of C 70 /syn-1 complex the axis lies perpendicularly to the line connecting two zinc atoms; however, for the C 70 /syn-2 complex, the axis occupies in-plane to the same line. Both the clefts of syn-1 and syn-2 are induced to fit the included fullerenes by domed out-of-plane distortion of porphyrin rings. Moreover, the bicyclo[2.2.2]octadiene moieties of syn-1 are widened by complexation with the fullerenes, while the same moieties of syn-2 are narrowed by the complexation. Therefore, syn-1 catches the fullerenes at the shallow part of the cleft. On the other hand, syn-2 catches the fullerenes at the bottom part of the cleft. NMR experiments of the complexes in THF-d 8 also support these orientations even in solution. © 2011 World Scientific Publishing Company.
  • Synthesis, structures and properties of benzoporphycenes and naphthoporphycenes
    Daiki Kuzuhara, Hiroko Yamada, Hiroko Yamada, Shigeki Mori, Tetsuo Okujima, Hidemitsu Uno, Journal of Porphyrins and Phthalocyanines, 15, (9/10) 930 - 942,   2011年09月01日, A series of benzoporphycenes and naphthoporphycenes and their zinc complexes were prepared from bicyclo[2.2.2]octadiene fused porphycenes by a retro-Diels-Alder reaction and their photophysical properties were studied. Free-base tetranaphthoporphycene was not soluble in common organic solvents, but zinc tetranaphthoporphycene was slightly soluble in pyridine and showed B- and Q-bands at 507 and 690 nm, respectively. Dinaphthoporphycene showed broad B- and Q-bands due to its lower symmetry. Tetrabenzo-, dibenzo-, and dinaphthoporphycenes showed fluorescence at 673, 654, and 670 nm with quantum yields of 0.32, 0.42, and 0.31, respectively, although their precursors were non-fluorescent. Zinc complexes of tetrabenzo-, dibenzo-, tetranaphtho-, dinaphthoporphycenes and their bicyclo[2.2.2] octadiene-fused precursors revealed moderate fluorescence with quantum yields of 0.150.37. The crystal structures of tetrabenzo- and dibenzoporphycenes showed herringbone structures, while the zinc tetrabenzoporphycene showed a hexagonal box-structure with six pyridine ligands inside. © 2011 World Scientific Publishing Company.
  • Synthesis and [2+2] cycloaddition with tetracyanoethylene of ene-diyne scaffolds bearing ferrocenes at the periphery
    Taku Shoji, Shunji Ito, Tetsuo Okujima, Noboru Morita, European Journal of Organic Chemistry, 2011, (26) 5134 - 5140,   2011年09月01日, The ene-diyne systems 1 and 2, possessing ferrocenyl groups at the periphery, were prepared by a simple one-pot Sonogashira-Hagihara coupling reaction of ethynylferrocene with 9-dibromomethylene-9H-fluorene (4) and 9,10-bis(dibromomethylene)-9,10-dihydroanthracene (5). Ene-diyne 1 reacted with tetracyanoethylene (TCNE) in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadduct, cyclobutene, to afford the corresponding 1,1,4,4-tetracyanobutadiene (TCBD) derivative 6 in good yield. The redox behavior of the ene-diyne compounds 1 and 2, and the TCBD derivative 6 was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their electrochemical oxidation properties with multi-electron transfer depending on the number of ferrocene units in the molecule, in addition to the two-electron reduction of the TCBD moiety in the case of TCBD derivative 6. Moreover, a significant color change was observed by visible spectroscopy under electrochemical oxidation conditions and under reduction conditions in the case of TCBD derivative 6. Ene-diyne systems with ferrocenyl groups at the periphery were prepared by theSonogashira-Hagihara reaction and reacted with tetracyanoethylene in a [2+2] cycloaddition reaction to afford the 1,1,4,4-tetracyanobutadiene derivative in goodyield. The redox behavior was examined by cyclic voltammetry and differential pulse voltammetry; significant color changes were observed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Tetrabenzodiazaporphyrin:
    Tetsuo Okujima, Guangnan Jin, Saika Otsubo, Shinji Aramaki, Noboru Ono, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Journal of Porphyrins and Phthalocyanines, 15, (7/8) 697 - 703,   2011年07月01日, Bicyclo[2.2.2]octadiene(BCOD)-fused diazaporphyrin was synthesized by the reaction of BCOD-fused dipyrromethane with sodium nitrite in acetic acid/ethanol in the presence of copper(II) acetylacetonate. This soluble precursor was converted into the semiconducting thin film of (tetrabenzodiazaporphyrinato) copper(II) by heating after fabrication via spin-coating. © 2011 World Scientific Publishing Company.
  • Synthesis and properties of functional π-expanded compounds prepared by thermal or photochemical conversion of the precursors
    Hiroko Yamada, Hiroko Yamada, Daiki Kuzuhara, Shuhei Katsuta, Tetsuo Okujima, Hidemitsu Uno, Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, 69, (7) 802 - 813,   2011年07月01日, This paper focuses on the synthesis of new aromatic compounds by thermal, photochemical, or oxidative cleavage reaction of the corresponding precursors. The precursor-methods are useful for the derivatization of the non-soluble aromatic compounds. We have applied retro Diels-Alder reactions for the preparation of new π-expanded porphyrinoid compounds such as [14]tribenzotriphyrin (2.1.1), tetrabenzoporphycene, dodecasubstituted porphycene, tetraanthraporphyin, butadiyne-linked tetrabenzoporphyrin dimer, and so on. We have investigated the photocleavage synthesis of pentacenes from the corresponding a-diketone precursors. This photoreaction enabled us to prepare 1,4,8,11-tetrasubstituted pentacene. The synthesis of new pentacene derivatives with electron-withdrawing substituents at 6,13-positions by oxidative cleavage reaction will be also reported.
  • Cyclo[8]isoindoles: Ring-expanded and annelated porphyrinoids
    Tetsuo Okujima, Guangnan Jin, Naoki Matsumoto, John MacK, Shigeki Mori, Keishi Ohara, Daiki Kuzuhara, Chie Ando, Noboru Ono, Hiroko Yamada, Hidemitsu Uno, Nagao Kobayashi, Angewandte Chemie - International Edition, 50, (25) 5699 - 5703,   2011年06月14日, Retro: Cyclo[8]isoindole, which has a saddle-shaped geometry (see picture, 2), was synthesized by oxidative coupling of a bicyclo[2.2.2]octadiene(BCOD)- fused 2,2′-bipyrrole followed by a retro-Diels-Alder reaction of BCOD-fused cyclo[8] pyrrole (1). Key trends in the optical spectra of ring-annelated cyclo[8]pyrroles are identified based on magnetic circular dichroism spectra and theorectical calculations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Synthesis of π-expanded O-chelated boron-dipyrromethene as an NIR dye
    Yuya Tomimori, Tetsuo Okujima, Tomoko Yano, Shigeki Mori, Noboru Ono, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Tetrahedron, 67, (18) 3187 - 3193,   2011年05月06日, A π-expanded BODIPY dye with an intramolecular boronate skeleton was synthesized by retro Diels-Alder reaction of the bicyclo[2.2.2]octadiene (BCOD)-fused BODIPY and the subsequent O-chelation. The photophysical and electrochemical properties were examined by UV-vis, fluorescence, CV measurements, and DFT calculation. This BODIPY exhibited the absorption and emission over a visible-NIR region at 600-850 nm. O-chelated BODIPY showed a bathocromic shift compared to F-BODIPYs. This dye showed a bright fluorescence emission at 733 nm with the high Φ value of 0.58. © 2011 Elsevier Ltd. All rights reserved.
  • Synthesis of redox-active, intramolecular charge-transfer chromophores by the [2+2] cycloaddition of ethynylated 2H-Cyclohepta[b]furan-2-ones with tetracyanoethylene
    Taku Shoji, Junya Higashi, Shunji Ito, Tetsuo Okujima, Masafumi Yasunami, Noboru Morita, Chemistry - A European Journal, 17, (18) 5116 - 5129,   2011年04月26日, Ethynylated 2H-cyclohepta[b]furan-2-ones 5-15 have been prepared by Pd-catalyzed alkynylation of 3-iodo-5-i sopropyl-2H-cyclohepta[b]furan-2-one (2) with the corresponding ethynylarenes or the reaction of 2-iodothiop hene with 3-ethynyl-5-isopropyl-2H-cyclohepta[b]furan-2-one (4) under Sonogashira-Hagihara conditions. Compounds 5-15 reacted with tetracyanoethylene in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadducts, cyclobutenes, to afford the corresponding 1,1,4,4- tetracyanobutadienyl (TCBD) chromophores 16-26 in excellent yields. The intramolecular charge-transfer interactions between the 2H-cyclohepta[b] furan-2- one ring and TCBD acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel TCBD derivatives 16-26 was examined by cyclic voltammetry and differential pulse voltammetry, which revealed multistep electrochemical reduction properties, depending on the number of TCBD units in the molecule. Moreover, a significant color change was observed by UV/Vis spectroscopy under electrochemical reduction conditions. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Ultrafast intramolecular energy relaxation dynamics of benzoporphyrins: Influence of fused benzo rings on singlet excited states
    Pyosang Kim, Jooyoung Sung, Hiroki Uoyama, Tetsuo Okujima, Hidemitsu Uno, Dongho Kim, Journal of Physical Chemistry B, 115, (14) 3784 - 3792,   2011年04月14日, We have investigated the role of fused benzo rings on the electronic structures and intramolecular energy relaxation dynamics in a series of benzoporphyrins (Bp1, syn-Bp2, anti-Bp2, Bp3, and Bp4) by using time-resolved fluorescence measurements and theoretical calculations. Interestingly, even though anti- and syn-Bp2 have the same number of fused benzo rings, in the respective absorption spectra, anti-Bp2 shows an obvious splitting of B x (Q x ) and B y (Q y ) states, whereas syn-Bp2 exhibits degenerate B and Q bands. These features provide two dynamical models for the effect of the position of substituted benzo rings on the intramolecular energy relaxation dynamics. syn-Bp2 gives rise to similar intramolecular dynamics from the B state to the Q state in the case of ZnTPP having D 4h molecular symmetry. On the other hand, anti-Bp2 shows split B and Q bands in the order B y > B x > Q x > Q y , which leads a superimposition of the Q x (0,0) and Q y (1,0) bands. This overlap generates a strong coupling between these two states, which results in a direct internal conversion from B x (0,0) to Q y (0,0). This observation suggests that the anti-type fused position of benzo rings leads to a new mechanism in internal conversion from the B to the Q state. On the basis of this work, further insight was obtained into the effect of fused benzo rings on the photophysical properties of benzoporphyrins, providing a detailed understanding of the structure-property relationship in a series of benzoporphyrins. © 2011 American Chemical Society.
  • Synthesis, properties, and ambipolar organic field-effect transistor performances of symmetrically cyanated pentacene and naphthacene as air-stable acene derivatives
    Shuhei Katsuta, Daichi Miyagi, Hiroko Yamada, Hiroko Yamada, Hiroko Yamada, Tetsuo Okujima, Shigeki Mori, Ken Ichi Nakayama, Ken Ichi Nakayama, Hidemitsu Uno, Organic Letters, 13, (6) 1454 - 1457,   2011年03月18日, 5,12-Dicyanonaphthacene and 6,13-dicyanopentacene have been synthesized for the first time. The LUMO and HOMO levels are deepened as predicted and fabricated organic field-effect transistors (OFETs) showed ambipolar responses with carrier mobilities of 10 -3 cm 2 /V•s. © 2011 American Chemical Society.
  • First synthesis of dodecasubstituted porphycenes
    Daiki Kuzuhara, Hiroko Yamada, Hiroko Yamada, Keiko Yano, Tetsuo Okujima, Shigeki Mori, Hidemitsu Uno, Chemistry - A European Journal, 17, (12) 3376 - 3383,   2011年03月14日, The synthesis of dodecasubstituted porphycenes has not been reported, to date. Herein, the preparation of tetramethyloctaethylporphycene by a McMurry-type coupling of 3,3′,4,4′-tetraethyl-5,5′-diformyl-2, 2′-bipyrrole was attempted at first, but dodecasubstituted porphycene was not successfully obtained and only pyrrolocyclophene was obtained. The structure of the pyrrolocyclophene was determined by 1 HNMR spectroscopy, FAB MS, and X-ray crystal-structure analysis. The pyrrolocyclophene was not successfully oxidized to porphycene. Then, the McMurry-type coupling of bicyclo[2.2.2]octadiene (BCOD)-fused 5,5′-diacyl-2,2′-bipyrroles was performed and tetra-meso-octa-β-substituted (dodecasubstituted) porphycenes were successfully obtained for the first time. The structures were determined by 1 HNMR spectroscopy and X-ray crystal-structure analysis. The crystal structures and NMR spectra were compared carefully with octasubstituted porphycenes, and there was a good correlation betw een the position of the substituents, the N1-N2 and N1-N4 distances of the porphycene inner nitrogen atoms, and NMR chemical shifts of the inner NH protons, which expressed the strength of N-H⋯N hydrogen bonding between N1 and N2. These results suggested that the BCOD structure was relatively compact compared with common alkyl groups and that was why the dodecasubstituted porphycenes were available this time. UV/Vis absorption and fluorescence properties are also discussed. Square versus rectangle: Dodecasubstituted porphycenes were prepared, for the first time, by taking advantage of the unique features of bicyclo[2.2.2]octadiene-fused 2,2′-dipyrroles. The retro-Diels-Alder reaction of dodecasubstituted porphycenes gave meso-substituted tetrabenzoporphycenes (see figure). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • New synthesis of meso-free-[14]triphyrin(2.1.1) by McMurry coupling and its derivatization to Mn(i) and Re(i) complexes
    Daiki Kuzuhara, Hiroko Yamada, Zhaoli Xue, Tetsuo Okujima, Shigeki Mori, Zhen Shen, Hidemitsu Uno, Chemical Communications, 47, (2) 722 - 724,   2011年01月14日, The metal-free and meso-free [14]triphyrin(2.1.1) compound was successfully prepared based on the intramolecular McMurry coupling reaction of diformyl-tripyrrane in 16% yield, and was converted to the bowl-shaped Mn(i)(TriP)(CO) 3 and Re(i)(TriP)(CO) 3 . © The Royal Society of Chemistry 2011.
  • Synthesis and redox behavior of Bis(3-methylthio-1-azulenyl)methyl Cations and dications connected by 2-thienyl and 2,5-thiophenediyl spacers
    Taku Shoji, Junya Higashi, Shunji Ito, Tetsuo Okujima, Noboru Morita, European Journal of Organic Chemistry, 2011, (3) 584 - 592,   2011年01月01日, Novel bis(3-methylthio-1-azulenyl)methyl cations 3a + and 3b + and dications 4a 2+ and 4b 2+ were synthesized by thehydride abstraction reaction of the corresponding hydride derivatives 7a, 7b, 8a, and 8b, which were readily prepared by the acid-catalyzed condensation reaction of 6a and 6b with the corresponding aldehyde and dialdehyde with DDQ. The pK R + values of novel cations 3a + and 3b + and dications 4a 2+ and 4b 2+ were determined spectrophotometrically to examine the thermodynamic stability of these carbocations. The redox behavior of the mono- and dications was also examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their reversible electrochemical reduction properties, except for the case of dication 4b 2+ . Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions. Dications 4a 2+ and 4b 2+ were also chemically reduced by Zn powder to afford thienoquinoid compounds 9a and 9b, respectively. Bis(3-methylthio-1-azulenyl)methyl cations and dications were synthesized from the corresponding hydride derivatives, which were prepared by the acid-catalyzed condensation reaction of 1-methylthioazulenes with aldehydes and dialdehydes with DDQ. These novel carbocations exhibited reversible electrochemical reduction properties. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Synthesis, crystal structure, and photodynamics of π-Expanded Porphyrin-Fullerene dyads synthesized by Diels-Alder reaction
    Hiroko Yamada, Hiroko Yamada, Kei Ohkubo, Daiki Kuzuhara, Tetsuro Takahashi, Atula S.D. Sandanayaka, Tetsuo Okujima, Keishi Ohara, Osamu Ito, Hidemitsu Uno, Noboru Ono, Shunichi Fukuzumi, Shunichi Fukuzumi, Journal of Physical Chemistry B, 114, (45) 14717 - 14728,   2010年12月08日, Free base and zinc porphyrins are linked with fullerene (C 60 ) through β,β′-pyrrolic positions rather than meso-positions by Diels-Alder reaction of monoanthraporphyrins (H 2 P-mA and ZnP-mA) and C 60 to afford a π-expanded free base porphyrin-fullerene dyad (H 2 P-C 60 ) and its zinc porphyrin-fullerene dyad (ZnP-C 60 ) in 86 and 51 % yield, respectively. The X-ray crystallographic analysis of ZnP-C 60 showed two comma-shaped swirls-like structure in a unit cell. The intramolecular center-to-center and edge-to-edge distances between the porphyrin and fullerene moieties were 11.5 and 2.5 Å, respectively. The porphyrins and fullerenes were packed in layer-by-layer structure and the porphyrins lied down in parallel, The intermolecular center-to-center distances between the neighboring fullerenes were 10.252, 10.028, and 10.129 Å, which were less than typical van der Waals distance and the π-π interaction spread two-dimensionally. The energy of the charge-separated (CS) state of ZnP-C 60 (1.11 eV) determined by differential-pulse voltammetry measurements in benzonitrile is significantly lower than those of zinc porphyrin-C 60 dyads linked at meso positions because of the low oxidation potential of the < -expanded ZnP moiety. The CS energy of ZnP-C 60 in a nonpolar solvent such as toluene (1.40 V) is lower than the triplet excited state of C 60 ( 3 C 60 *), enabling us to attain a longed lived triplet CS state (8.1 μs) in toluene, detected by nanosecond laser flash photolysis experiments. The distance between unpaired electrons in the triplet CS state was determined by the EPR spectrum to be 9.1 Å, which agreed with the distance between a zinc atom of the porphyrin and a carbon edge of C 60 in the crystal structure of ZnP-C 60 . The rate constants of photoinduced electron transfer and back electron transfer of H 2 P-C 60 and ZnP-C 60 , which were determined by femtosecond and nanosecond laser flash photolysis measurements, were analyzed in light of the Marcus theory of electron transfer. © 2010 American Chemical Society.
  • Synthesis and properties of BCOD-fused trithiasapphyrin and trithiabenzosapphyrins
    Tetsuo Okujima, Tasuku Kikkawa, Saori Kawakami, Yusuke Shimizu, Hiroko Yamada, Noboru Ono, Hidemitsu Uno, Tetrahedron, 66, (35) 7213 - 7218,   2010年08月28日, Bicyclo[2.2.2]octadiene(BCOD)-fused trithiasapphyrin was prepared by 3+2 condensation of BCOD-fused thiatripyrrane with BCOD-fused bithiophene. The BCOD-fused trithiasapphyrin was successfully converted to pentabenzo[b,g,l,q,v] sapphyrin by the thermal retro-Diels-Alder reaction. In this case, trithiapentabenzo[b,g,l,q,v]- and trithiadibenzo[g,q] sapphyrins were selectively prepared by control of the temperature in the thermal retro-Diels-Alder reaction. © 2010 Elsevier Ltd.
  • Synthesis of π-expanded BODIPYs and their fluorescent properties in the visible-near-infrared region
    Tetsuo Okujima, Yuya Tomimori, Jun Nakamura, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Tetrahedron, 66, (34) 6895 - 6900,   2010年08月21日, A series of π-expanded boron-dipyrromethenes (BODIPYs) fused with aromatic rings at β,β-positions, such as benzene, acenaphthylene, and benzofluoranthene were prepared by the reaction of BF 3 · OEt 2 with bicyclo[2.2.2]octadiene-fused dipyrromethene and the subsequent retro Diels-Alder reaction. These BODIPYs exhibited the absorptions and the fluorescence emissions over wide range of visible-near-infrared region at 500-800 nm. BODIPYs composed of two fluorantho[8,9-f] isoindoles absorbed and emitted at red-region over 750 nm with absolute fluorescence quantum yield (Φ f ) of ca. 0.3, although they are unstable under air in room light. BODIPY composed fluorantho[8,9-f]isoindole and acenaphtho[1,2-c] pyrrole was stable and showed a bright fluorescence emission at 695 nm with high Φ f of 0.70. © 2010 Elsevier Ltd. All rights reserved.
  • Pentacene precursors for solution-processed OFETs
    Hiroki Uoyama, Hiroko Yamada, Tetsuo Okujima, Hidemitsu Uno, Tetrahedron, 66, (34) 6889 - 6894,   2010年08月21日, 15-Acetoxy- and 15-hydroxy-6,13-dihydro-6,13-ethanopentacenes sublimed over 300 °C and no pentacene was formed below the temperature. The precursors bearing chlorinated epithiomethano bridges suffered complicated decomposition to give oligomeric pentacene derivatives. The precursor bearing an epithio-oxomethano bridge underwent smooth and clean conversion to pentacene by heat or light. An organic field-effect transistor fabricated by the spin-coating method of the precursor followed by light irradiation at 120 °C showed a good FET performance of μ=2.5×10 -2 cm 2 V -1 s -1 and on/off ratio=3.8×10 4 . © 2010 Elsevier Ltd. All rights reserved.
  • Synthesis of 2,3-dihydrobenzo[1,4]dithiin-fused porphyrins
    Guangnan Jin, Tetsuo Okujima, Yusuke Hashimoto, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Phosphorus, Sulfur and Silicon and the Related Elements, 185, (5-6) 1108 - 1116,   2010年05月01日, This article describes the preparation of (ethylenedithio)bicyclo[2.2.2] octadiene-fused porphyrins 13 and 14a,b as soluble precursors of 2,3-dihydrobenzo[1,4] dithiin-fused porphyrins and the retro Diels-Alder conversion of the precursors 13 and 14a,b. Copyright © Taylor & Francis Group.
  • Highly pure synthesis, spectral assignments, and two-photon properties of cruciform porphyrin pentamers fused with benzene units
    Hiroki Uoyama, Kil Suk Kim, Kenji Kuroki, Jae Yoon Shin, Toshi Nagata, Tetsuo Okujima, Hiroko Yamada, Noboru Ono, Dongho Kim, Hidemitsu Uno, Chemistry - A European Journal, 16, (13) 4063 - 4074,   2010年04月06日, Tetrameric porphyrin formation of 2-hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2] octadiene- fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π-conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π-conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyr-ins. From TD-DFT calculations, the HOMO level is 0.49 eV higher than the HOMO-1 level. The LUMO and LUMO+ 1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single-electron transitions (683 nm: 86%, HOMO LUMO; 680 nm: 86%, HOMO- > LUMO + 1). The two-photon absorption (TPA) cross section value (σ( 2 )) of the benzene-fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π-conjugation pathways. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.
  • Synthesis and photochemical properties of α-diketoporphyrins as precursors for π-expanded porphyrins
    Hiroko Yamada, Hiroko Yamada, Daiki Kuzuhara, Kei Ohkubo, Tetsuro Takahashi, Tetsuo Okujima, Hidemitsu Uno, Noboru Ono, Shunichi Fukuzumi, Shunichi Fukuzumi, Journal of Materials Chemistry, 20, (15) 3011 - 3024,   2010年04月06日, A new α-diketoporphyrin and the corresponding Pd complex were prepared from the monoanthroporphyins and their photochemical properties were investigated by measurements of absorption and emission spectra, fluorescence lifetimes, laser flash photolysis, cyclic voltammetry , and theoretical calculations. Intramolecular electron transfer from the porphyrin singlet excited state to the diketone moiety was observed for the free base α-diketoporphyrin in benzonitrile, but this was not observed in toluene. Photoreactivity of the α-diketoporphyrins was also examined by irradiation at the Soret and Q bands. When the Soret band of the freebase α-diketoporphyrin was irradiated, cleavage of the diketone moiety occurred to afford the monoanthroporphyrin with the release of two CO molecules quantitatively in both benzonitrile and toluene. When the Q band of the freebase α-diketoporphyrin was irradiated, no photocleavage reaction occurred in toluene. In contrast to the freebase α-diketoporphyrin, the photocleavage reaction of the Pd complex occurred with irradiation at the Q band as well as the Soret band to afford the monoanthroporphyrin quantitatively in toluene. The photocleavage reaction proceeded much more effectively in toluene than in benzonitrile. The occurrence of rapid photoinduced electron transfer from the singlet excited state porphyrin to the diketone moiety, which was detected by femtosecond laser flash photolysis measurements, results in a significant decrease in the singlet excited state lifetime, prohibiting the photocleavage reaction in benzonitrile. Thus, the Pd α-diketoporphyrin can act as an excellent precursor for the corresponding acene in toluene. The photocleavage process provides a convenient and inexpensive method to make the thin film. © The Royal Society of Chemistry.
  • Photochemical synthesis of tetraaryl-substituted pentacenes
    Shuhei Katsuta, Hiroko Yamada, Hiroko Yamada, Tetsuo Okujima, Hidemitsu Uno, Tetrahedron Letters, 51, (10) 1397 - 1400,   2010年03月10日, The syntheses of 1,4,8,11-tetraphenylpentacene and 1,4,8,11-tetra(2′-thienyl)pentacene are described via photodecarbonylation of the corresponding α-diketone precursors. © 2010 Elsevier Ltd. All rights reserved.
  • Thermal behavior of bicyclo[2.2.2]octadiene-installed precursors for 2H-anthra[2,3-c]pyrroles and anthra[2,3-c]thiophene
    Hiroki Uoyama, Cai Chenxin, Cai Chenxin, Hiroyuki Tahara, Yusuke Shimizu, Hideki Hagiwara, Yasuaki Hanasaki, Hiroko Yamada, Hiroko Yamada, Tetsuo Okujima, Hidemitsu Unoa, Hidemitsu Unoa, Heterocycles, 80, (2) 1187 - 1196,   2010年03月01日, 4,11-Ethano-4,11-dihydro-2H-anthra[2,3-c]pyrrole and 4,11-ethano-4,11- dihydroanthra[2,3-c] thiophene derivatives were prepared from the corresponding bicyclo[2.2.2]octadiene-fused five-membered heterocycles by the Diels-Alder reaction with in situ generated α,α′-dibromo-o-xylylene derivatives. Their thermogravimetric analyses showed evapolation without formation of 2H-anthra[2,3-c] pyrrole and anthra[2,3-c]thiophene derivatives under the atmospheric pressure. © 2010 The Japan Institute of Heterocyclic Chemistry Received.
  • Synthesis of tetrabenzoporphyrins fused with fluoranthenes
    Jun Nakamura, Tetsuo Okujima, Yuya Tomimori, Naoki Komobuchi, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Heterocycles, 80, (2) 1165 - 1175,   2010年03月01日, Tetrabenzoporphyrins fused with fluoranthenes were prepared by the retro Diels-Alder reaction of the precursors composed of a porphyrin and four fluoranthenes connected with bicyclo[2.2.2]octadiene (BCOD). These porphyrins exhibited the Soret (480-494 nm, ε = 243,000277,000) and intense Q bands (739760 nm, ε = 375,000-509,000). Free bases and Zn complexes of them fluoresce at 760 nm and 746 nm with small Storks shifts and high quantum yields of 30 and 10 %, respectively. © 2010 The Japan Institute of Heterocyclic Chemistry Received.
  • Absorption and emission properties of acenaphthoporphyrins
    Jun Nakamura, Noboru Ono, Hiroko Yamada, Hiroko Yamada, Tetsuo Okujima, Molecular Crystals and Liquid Crystals, 505,   2009年12月01日, Acenaphtho[1,2-b]porphyrins (AcePs) were prepared by the [3+1] condensation method and their photochemical properties were investigated. The fluorescence spectra of the free-base AcePs in CHCl 3 showed two emission bands at 660 and 720 nm, whose intensity drastically changed depending on the excitation wavelength. However, those of zinc complexes did not show such a wavelength dependence and showed similar emission spectra by the excitation at various wavelengths. The fluorescence excitation spectra and quantum yields of the free-base AcePs in CHCl 3 showed the similar excitation wavelength dependence. This fact indicates that two electronic structures exist in the free-base AcePs and their fluorescence is emitted from one structure in higher quantum yield (λ EM =660 nm) and from the other in lower yield (λ EM =720 nm), respectively. Copyright © Taylor & Francis Group, LLC.
  • Towards the preparation of electrochromic materials with strong absorption in the near-infrared region: Synthesis and redox behavior of azulene-substituted enediyne scaffolds connected by a 9,10-anthracenediyl spacer
    Shunji Ito, Takahiro Iida, Jun Kawakami, Tetsuo Okujima, Noboru Morita, European Journal of Organic Chemistry, 2009, (31) 5355 - 5364,   2009年11月01日, Enediyne scaffolds connected by a 9,10-anthracenediyl spacer as a redox-active substructure with 6-azulenyl groups as π-electron-accepting groups in their periphery (3a and 3b) have been prepared by a one-pot reaction involving repeated Pd-catalyzed alkynylation of 6-haloazulenes 7b and 7c with bis(enediyne) derivative 6. The azulene-substituted bis(enediyne)s 3a and 3b exhibited two reversible one-step, two-electron reduction properties upon cyclic voltammetry (CV) attributable to the formation of dianionic and tetraanionic species. The electrochemical reduction of 3a and 3b led a strong absorption in the near-IR region corresponding to the formation of the stabilized dianionic species 3a RED 2- and 3b RED 2- . An electrochromic analysis revealed the lower stability of the tetraanionic species 3a RED 4- and 3b RED 4- , although the CV exhibited good reversibility. The mono(enediyne) systems 11a and 11b were also prepared for comparison. The electrochemical reduction of 11a and 11b did not exhibit good electrochemical reversibility by CV, but the electrochemical reduction led to a strong absorption in the near-IR region, similar to the formation of the stabilized dianionic species 3a RED 2- and 3b RED 2- in the bis(enediyne) systems. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
  • Synthesis, structures, and optical and electrochemical properties of benzoporphycenes
    Daiki Kuzuhara, John Mack, Hiroko Yamada, Hiroko Yamada, Tetsuo Okujima, Noboru Ono, Nagao Kobayashi, Chemistry - A European Journal, 15, (39) 10060 - 10069,   2009年10月05日, The first facile syntheses of free-base di- and tetrabenzoporphycenes and their metal complexes are reported, based on retro-Diels-Alder reactions of the corresponding bicyclo[2.2.2]octadiene-fused porphycenes, prepared by McMurray coupling of α,α'-diformyldipyrrole. The photophysical and electrochemical properties are analyzed based on UV/Vis absorption, magnetic circular dichroism (MCD), and fluorescence emission, lifetime and quantum yield measurements, cyclic and differential pulse voltammetry (CV and DPV) and time-dependent DFT calculations based on B3LYP geometry optimizations. Benzoporphycenes are found to be prime candidates for future use in photodynamic therapy. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
  • First synthesis of porphyrin-fused 1,10-phenanthroline-ruthenium(II) complexes
    Tetsuo Okujima, Akihlro Mifuji, Jun Nakamura, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Organic Letters, 11, (18) 4088 - 4091,   2009年09月17日, Synthesis of [Ru(phenP) 3 ](PF 6 ) 2 , where phenP = phenanthrolinoporphyrin, has been achieved by the reaction of phenanthrolinoporphyrins with RuCl 3 for the first time. The phenP reacted with Ru(II) to form RuL 2 (phenP) 2+ complexes (L = 2,2'-bipyridine or 1,10-phenanthroline), which were converted into the dyads Ru-phenP(Zn) on treatment with zinc acetate. © 2009 American Chemical Society.
  • 1-Aminoisoindole as a useful π-system elongation unit
    Taiji Akiyama, Hiroki Uoyama, Tetsuo Okujima, Hiroko Yamada, Hiroko Yamada, Noboru Ono, Hidemitsu Uno, Tetrahedron, 65, (22) 4345 - 4350,   2009年05月30日, Nitration of 4,7-ethanoisoindoles gave 1-nitro derivatives in moderate yields. Reduction of a nitro to amino group was successfully performed by sodium hydrosulfite in the case of ethyl 3-nitro-4,7-ethanoisoindole-1-carboxylate. The amino derivative was converted to benzylidenaminoisoindoles based on the retro Diels-Alder reaction. Their UV-vis spectra showed strong absorptions at 500-700 nm. © 2009 Elsevier Ltd. All rights reserved.
  • Organic thin-film transistor from a pentacene photoprecursor
    Akane Masumoto, Yuko Yamashita, Shintetsu Go, Toshihiro Kikuchi, Hiroko Yamadao, Tetsuo Okujima, Noboru Ono, Hidemitsu Uno, Japanese Journal of Applied Physics, 48, (5,Issue 1) 1 - 51505,   2009年05月01日, Organic thin-film transistors were successfully fabricated by the spin-coating method using a photo-precursor of pentacene, 6,13-dihydro- 6,13-ethanopentacene-15,16-dione. After spin coating the soluble precursor, irradiation with visible light gave a pentacene film. A good mobility of 0.34cm2 V -1 s -1 and a high on/off ratio of 2.0 - 106 were achieved by treatment of the insulator surface with methyl silsesquioxane and by deposition of pentacene from the precursor with visible light irradiation ( > 300 nm) and mild heat treatment (110-120 °C). In this case, small grains of pentacene crystals existed in the loosely ordered pentacene mesophase, in which pentacene molecules aligned vertically. Not only the grains of pentacene crystals but also the loosely packed pentacene phase played an important role in the field-effect transistor (FET) performance. © 2009 The Japan Society of Applied Physics.
  • Electrophilc ipso-substltiitlon and some unique reaction behavior of 1,3,6-tri-tri-butylazulene
    Taku Shoji, Shunji Ito, Tetsuo Okujima, Junya Higashi, Ryuji Yokoyama, Kozo Toyota, Masafumi Yasunami, Noboru Morita, European Journal of Organic Chemistry,   2009年04月01日, Electrophilic ipso-substitution reactions between 1,3,6-tritert- butylazulcne (2) and several electrophilic reagents were examined. Friedel-Crafts and Vilsmeier reactions of 2 gave the corresponding ipso-substitution products in moderate to excellent yields. One of the ipso-substitution products, 1,6- di-tert-butyl-3-formylazulene (5), was converted in high yield into the synthetically more useful azulene derivative 1,6-di-tert-butylazulene (1) by decarbonylation on treatment with pyrrole in acetic acid. Treatment of 2 with N-[(trifluoromelhyl)su]fonyl] pyridinium trifluoromethanesulfonate (TPT) unexpectedly afforded 1- trifluoromethylthioazulene 10 and l(8H)-azulenone 11. Compound 2 also reacted with tetracyanoethylene (TCNE) to give an excellent yield of cycloaddition product 13, rather than the ipso-substitution reaction product. © Wiley-VCH Verlag GmbH & Co. KGaA.
  • Synthesis of mono-, di- and tribenzoporphyrins from their soluble precursors
    Tetsuo Okujima, Yusuke Hashimoto, Guangnan Jin, Hiroko Yamada, Hiroko Yamada, Noboru Ono, Heterocycles, 77, (2) 1235 - 1248,   2009年02月01日, Soluble precursors of β-, meso-unsubstituted mono-, di- and tribenzoporphyrins were prepared by the reaction of dimethylbicyclo[2.2.2] octadiene-fused pyrrole with appropriate β-free pyrroles. The retro Diels-Alder reaction of these precursors afforded the corresponding benzoporphyrins in quantitative yields. © 2009 The Japan Institute of Heterocyclic Chemistry All rights reserved.
  • A facile one-pot synthesis of meso-aryl-substituted [14]triphyrin(2.1.1)
    Zhao Li Xue, Zhen Shen, John Mack, Daiki Kuzuhara, Hiroko Yamada, Tetsuo Okujima, Noboru Ono, Xiao Zeng You, Nagao Kobayashi, Journal of the American Chemical Society, 130, (49) 16478 - 16479,   2008年12月10日, The synthesis and spectroscopic properties of a series of boron-free meso-aryl-substituted [14]triphyrin(2.1.1) compounds containing either peripheral bicyclo[2.2.2] octadiene (BCOD) (2a-c) or benzene rings (3a-c) (aryl = phenyl a, 4-fluorophenyl b, and 4-methylbenzoatephenyl c) are reported. These compounds represent the first examples of free-base contracted porphyrinoids with 14 π-electron aromatic systems containing only the standard pyrrole and isoindoline moieties of the porphyrins and tetrabenzoporphyrins. Copyright © 2008 American Chemical Society.
  • Synthesis and characterization of tetraanthroporphyrins
    Hiroko Yamada, Hiroko Yamada, Daiki Kuzuhara, Tetsuro Takahashi, Yusuke Shimizu, Keisuke Uota, Tetsuo Okujima, Hidemitsu Uno, Noboru Ono, Organic Letters, 10, (14) 2947 - 2950,   2008年12月01日, (Chemical Equation Presented) Linearly π-expanded novel tetraanthroporphyrins with and without aromatic rings at the meso-positions were prepared quantitatively for the first time from the corresponding precursors by a retro-Diels-Alder reaction. © 2008 American Chemical Society.
  • Soluble precursors of 2,3-naphthalocyanine and phthalocyanine for use in thin film transistors
    Atsuko Hirao, Taiji Akiyama, Tetsuo Okujima, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Yoshimasa Sakai, Shinji Aramaki, Noboru Ono, Chemical Communications, (39) 4714 - 4716,   2008年10月09日, Soluble precursors of 2,3-naphthalocyanine (Nc) and phthalocyanine (Pc) were prepared and were converted into insoluble semiconducting thin films of Pc and Nc by heating after fabrication via spin-coating. © The Royal Society of Chemistry.
  • Selective synthesis of 5-alkenyl-15-alkynyl-porphyrin and 5,15-dialkynyl-porphyrin by 2+2 acid-catalyzed condensation of dipyrrylmethane and TMS propynal
    Hiroko Yamada, Hiroko Yamada, Kayo Kushibe, Satoshi Mitsuogi, Tetsuo Okujima, Hidemitsu Uno, Noboru Ono, Tetrahedron Letters, 49, (32) 4731 - 4733,   2008年08月04日, One of 5-alkenyl-15-alkynyl-porphyrin and 5,15-dialkynyl-porphyrin was prepared selectively by 2+2 acid-catalyzed condensation of bicyclo[2.2.2]octadiene-fused dipyrrylmethane and TMS propynal in the presence of BF 3 ·OEt 2 only by the choice of the solvent. The alkenyl group was expected to be obtained by a protonation followed by intramolecular 1,2-hydride transfer from methine position of porphyrinogen. © 2008 Elsevier Ltd. All rights reserved.
  • Organic semiconductors based on small molecules with thermally or photochemically removable groups
    Hiroko Yamada, Hiroko Yamada, Tetsuo Okujima, Noboru Ono, Chemical Communications, (26) 2957 - 2974,   2008年07月07日, Solution processable organic semiconducting small molecules are desirable for the manufacture of low-cost, large-area electronic products on flexible substrates. This article provides an overview of recent progress in OFETs based on solution processable small molecules that can be converted to insoluble organic semiconducting materials on films by thermal or photochemical removal of leaving groups after fabrication of the film. © The Royal Society of Chemistry.
  • Application of MCD spectroscopy and TD-DFT to nonplanar core-modified tetrabenzoporphyrins: Effect of reduced symmetry on nonplanar porphyrinoids
    John Mack, John Mack, Masaru Bunya, Yusuke Shimizu, Hiroki Uoyama, Naoki Komobuchi, Tetsuo Okujima, Hidemitsu Uno, Satoshi Ito, Martin J. Stillman, Noboru Ono, Nagao Kobayashi, Chemistry - A European Journal, 14, (16) 5001 - 5020,   2008年05月29日, The optical spectra of a series of core-modified tetrabenzoporphyrins were analyzed to determine the effects of core modification, ligand folding, and partial benzo substitution at the ligand periphery on the electronic structure by using magnetic circular dichroism (MCD) and NMR spectroscopy, X-ray crystallography, cyclic and differential pulse voltammetry, and TD-DFT calculations. Planar 21-carba-, 21-thia-, 21,23-dithia-, and 21-oxa-23-thiatetrabenzo[b,g,l,q]porphyrins reported previously were studied together with the previously unreported 21-oxa- and 21-carba-23-thiatetrabenzo- [b,g,l,q] porphyrins. The optical properties of these compounds are compared to those of tetrabenzo[b,g,l,q]-, 5,10,15,20-tetraphenyl-, 5,10,15,20 -tetraphenyltetrabenzo[b,g,l,q] -21-thia-, 5,10,15,20- tetraphenyltetrabenzodithia-, 5,10,15,20-tetraphenyldibenzo[g,q]-21,23-dithia-, 5,10,15,20-tetraphenyldibenzo[b,l] -21,23-dithia-, 5,10,15,20- tetraphenyltribenzo[g,q,l]-21 -thia-, and 5,10,15,20-tetraphenylbenzo[b] -21- thiaporphyrins. Michl's perimeter model and Gouterman's four-orbital model are used to conceptualize the results and to account for red shifts commonly observed in the spectral bands of non-planar porphyrinoids. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
  • Synthesis and intramolecular pericyclization of 1-azulenyl thioketones
    Shunji Ito, Tetsuo Okujima, Shigeru Kikuchi, Taku Shoji, Noboru Morita, Toyonobu Asao, Tadaaki Ikoma, Tadaaki Ikoma, Shozo Tero-Kubota, Jun Kawakami, Akio Tajiri, Journal of Organic Chemistry, 73, (6) 2256 - 2263,   2008年03月21日, Several azulene-substituted thioketones, 1-thiobenzoylazulene (1a) and di(1-azulenyl) thioketone (2a) and their derivatives (1b and 2b-d) with alkyl substituents on each azulene ring, were prepared and their intramolecular pericyclization reaction was examined. The thioketones with a 3-alkyl substituent on each azulene ring exhibited the presumed pericyclization reaction under thermal and acid-catalyzed conditions, although the cases of the 1-azulenyl thioketones without the 3-alkyl substituents afforded a complex mixture under similar conditions. The intramolecular reaction following the intramolecular hydrogen transfer afforded the products 13b, 14b, and 14c. The products 13b and 14b were converted into the corresponding cations 18 + and 19 + , which have structural similarity with that of the phenalenyl cation. These cations exhibited the expected two-step reduction waves upon CV, although the ESR analysis revealed that the neutral radical state did not have the presumed high stability. © 2008 American Chemical Society.
  • Synthesis of extremely soluble precursors of tetrabenzoporphyrins
    Tetsuo Okujima, Yusuke Hashimoto, Guangnan Jin, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Tetrahedron, 64, (10) 2405 - 2411,   2008年03月03日, This paper describes the preparation of dimethylbicyclo[2.2.2]octadiene-fused porphyrins as extremely soluble precursors of tetrabenzoporphyrins and thermal conversion of the precursors to tetrabenzoporphyrins. © 2008 Elsevier Ltd. All rights reserved.
  • Thermal behavior of free-base and core-modified bicyclo[2.2.2]octadiene- fused porphyrins
    Hidemitsu Uno, Yusuke Shimizu, Hiroki Uoyama, Yousuke Tanaka, Tetsuo Okujima, Noboru Ono, European Journal of Organic Chemistry, 2008, (1) 87 - 98,   2008年01月15日, Multistep thermal fragmentation of quadruply bicyclo[2.2.2]-octadiene-fused porphyrins giving tetrabenzoporphyrins was examined in detail. After the first extrusion of an ethylene molecule from the porphyrin derivative, the opposite bicyclo[2.2.2] octadiene moiety preferentially underwent the second retro-Diels-Alder reaction to give an opp-dibenzoporphyrin derivative rather than an adj-dibenzoporphyrin derivative. These two benzoporphyrin derivatives then decomposed to give a tribenzoporphyrin derivative in similar rates. The temperature regions of these fragmentations could not be distinguished by thermogravimetric analysis. In contrast, the third and the fourth fragmentations obviously occurred stepwise. There was a temperature region where the tribenzoporphyrin derivative preferentially existed. In the case of the 21,23-dithiaporphyrin derivative, opp-21,23-dithiadibenzoporphyrin, possessing benzo moieties fused at the pyrrole parts of the core-modified porphyrin chromophore was predominantly formed during the fragmentation. In the case of the 21-thiaporphyrin derivative, an ethylene molecule was extruded selectively from the bicyclo[2.2.2]octadiene moiety adjacent to the thiophene part to give 21-thiabenzo[q] porphyrin and then 21-thiabenzo[g,q]porphyrin derivatives. In these cases, the last ethylene extrusion also occurred very slowly. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
  • Synthesis of phthalocyanine fused with bicyclo[2.2.2]octadienes and thermal conversion into naphthalocyanine
    Taiji Akiyama, Atsuko Hirao, Tetsuo Okujima, Hiroko Yamada, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Heterocycles, 74,   2007年12月31日, Mg complex of phthalocyanine fused with bicyclo[2.2.2]octadiene (BCOD) units is prepared by the reaction of BCOD-fused phthalonitrile with Mg(OPr) 2 in PrOH at 100 °C overnight in 42% yield. Subsequent heating the product at 250 °C results in clean formation naphthalocyanine via the retro Diels-Alder reaction. An attempt to the synthesis of BCOD-fused tetraazaporphyrin by the similar cyclization of the Diels-Alder adduct of dicyanoacetylene with 1,3-cyclohexadiene was unsuccessful. © 2007 The Japan Institute of Heterocyclic Chemistry.
  • Photocurrent generation by benzoporphyrin films prepared by a solution process
    Hiroko Yamada, Hiroko Yamada, Naoko Kamio, Akihiro Ohishi, Manami Kawano, Tetsuo Okujima, Noboru Ono, Journal of Porphyrins and Phthalocyanines, 11,   2007年07月17日, Tetrabenzoporphyrin films on indium-tin-oxide electrodes were prepared by continuous spin-coating of indium-tin-oxide electrodes with a soluble precursor, tetrabicyclo[2.2.2]octadiene-fused porphyrin, and subsequent thermal conversion of the precursor to tetrabenzoporphyrin by annealing the modified electrodes. When the tetrabenzoporhyrin-modified indium-tin-oxide working electrode was irradiated in a three-electrode system, using Pt as a counter electrode and Ag/Ag + as a reference electrode in the presence of hexyl viologen as an electron acceptor, a cathodic photocurrent was observed. A double layer structure consisting of tetrabenzoporphyrin and [6,6]-phenyl-C 61 butyric acid methyl ester (PCBM) films and a triple layer structure consisting of tetrabenzoporphyrin; a mixture of tetrabenzoporphyrin and PCBM; and PCBM films were also prepared on indium-tin-oxide electrodes by repeated spin-coating. The incident photon to photocurrent efficiency values of up to 6.8% were obtained for the triple layer structure, in which the mixed layer contained tetrabenzoporphyrin and PCBM molecules in a 7:3 ratio. Action spectra of the triple layer structure showed that visible light from 380 to 700 nm sensitized the system for photocurrent generation. Copyright © 2007 Society of Porphyrins & Phthalocyanines.
  • Synthesis, crystal structures and spectroscopic characterizations of two difluoroboradiaza-s-indacene dyes
    Yan Hong Yu, Zhen Shen, Hai Yun Xu, Hai Yun Xu, Yan Wei Wang, Tetsuo Okujima, Noboru Ono, Yi Zhi Li, Xiao Zeng You, Journal of Molecular Structure, 827, (1-3) 130 - 136,   2007年02月17日, Two new 8-(4-dimethylaminophenyl) substituted boron-dipyrromethene (BDP) dyes: 1,2,6,7-tetraethyl-4,4-difluoro-3,5-dimethyl-8-(4-dimethylaminophenyl)-4-bora-3a,4a-diaza-s-indacene (5) and 4,4-difluoro-1,2,3,5,6,7-hexamethyl-8-(4-dimethylaminophenyl)-4-bora-3a,4a-diaza-s-indacene (6) have been synthesized and their crystal structures are determined by X-ray diffraction analysis. The torsion angles of 8-phenyl ring and the indacene plane are 79.61° for 5 and 87.56° for 6, respectively. The absorption and steady-state fluorescence properties in different solvents have been investigated. The fluorescence quantum yields of the two dyes are lower in more polar solvents, which can be ascribed to the intramolecular charge transfer from the aniline to the BDP unit. Protonation of the aniline moiety at low pH in MeOH-H 2 O (1:1 v/v) solution causes a large fluorescence enhancement. The pK a values calculated from the pH dependent fluorescence emission spectra are 3.14 for 5 and 3.09 for 6, respectively. They are suitable as pH probes excitable with visible light. © 2006 Elsevier B.V. All rights reserved.
  • Synthesis of 4,7-dihydro-2H-isoindole derivatives via diels-alder reaction of tosylacetylene
    Tetsuo Okujima, Guangnan Ji, Yusuke Hashimoto, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Heterocycles, 70,   2006年12月31日, Diels-Alder reaction of ethynyl p-tolyl sulfone with 1,3-dienes gave the corresponding tosyl-1,4-cyclohexadienes. The resulting adducts could be converted into 4,7-dihydro-2H-isoindole derivatives including bicyclo[2.2.2]ocatadiene(BCOD)-fused pyrrole as an isoindole equivalent. © 2006 The Japan Institute of Heterocyclic Chemistry.
  • A new synthesis of tetra(quinoxalino)tetraazaporphyrin by the retro Diels-Alder reaction of a soluble precursor
    Tetsuo Okujima, Makoto Kikuchi, Hiroko Yamada, Hidemitsu Uno, Noboru Ono, Journal of Porphyrins and Phthalocyanines, 10,   2006年12月01日, Soluble tetra(pyrazino)tetraazaporphyrin was synthesized by the reaction of bicyclo[2.2.2]octadiene-fused dicyanopyrazine. The retro Diels-Alder reaction of the soluble tetra(pyrazino)tetraazaporphyrin gave a tetra(quinoxalino) tetraazaporphyrin in quantitative yield. Copyright © 2006 Society of Porphyrins & Phthalocyanines.
  • Effective photochemical synthesis of an air-stable anthracene-based organic semiconductor from its diketone precursor
    Hiroko Yamada, Emi Kawamura, Sadaaki Sakamoto, Yuko Yamashita, Tetsuo Okujima, Hidemitsu Uno, Noboru Ono, Tetrahedron Letters, 47, (42) 7501 - 7504,   2006年10月16日, A diketone precursor of air-stable bis-2-thienyl-2,6-anthracene was prepared and quantitatively converted to the target acene by photoirradiation of the n-π * absorption both in solution and as a film, in air. © 2006 Elsevier Ltd. All rights reserved.
  • Fluorescent probe for Na+: Synthesis and spectroscopic studies of exocyclic ring-fused boron dipyrromethene dyes
    Hai Yun Xu, Hai Yun Xu, Zhen Shen, Tetsuo Okujima, Noboru Ono, Chinese Journal of Inorganic Chemistry, 22,   2006年05月01日, Two new exocyclic ring-fused boron-dipyrromethene (BDP) dyes with benzo crown ether subunit at meso-position were prepared. Their spectroscopic and electroch emical properties were investigated. The introduction of the electron withdrawing ester groups to the chromophore makes compound 2 to be a very sensitive fluorescent probe for Na + analysis.
  • Novel one-pot synthesis of 5-alkenyl-15-alkynylporphyrins and their derivatisation to a butadiyne-linked benzoporphyrin dimer
    Hiroko Yamada, Kayo Kushibe, Tetsuo Okujima, Hidemitsu Uno, Hidemitsu Uno, Noboru Ono, Chemical Communications, (4) 383 - 385,   2006年04月06日, 5-Alkenyl-15-alkynylporphyrins have been obtained unexpectedly by [2 + 2] acid-catalyzed condensation of dipyrrylmethane and TMS propynal in addition to 5,15-dialkynylporphyrin, and the unsymmetrical porphyrin can be converted to a butadiyne-linked dimer by selective desilylation of the alkynyl TMS. © The Royal Society of Chemistry 2006.
  • Synthesis and spectroscopic characterization of meso-tetraarylporphyrins with fused phenanthrene rings
    Hai Jun Xu, Zhen Shen, Tetsuo Okujima, Noboru Ono, Xiao Zeng You, Tetrahedron Letters, 47, (6) 931 - 934,   2006年02月06日, A series of meso-tetraaryl porphyrins with fused phenanthrene rings have been synthesized from boron trifluoride-catalyzed Lindsey condensation of phenanthro[9,10-c]pyrrole with various para-substituted arylaldehydes at low temperature. Their structures were characterized by UV-vis, 1 H NMR, and mass spectroscopies. The UV-vis spectra of these compounds showed remarkable bathochromic shift of the Soret band to the wavelength around 577 nm and Q-bands into the near-infrared region. © 2005 Elsevier Ltd. All rights reserved.
  • A new synthesis of acenaphthobenzoporphyrin and fluoranthobenzoporphyrin
    Tetsuo Okujima, Naoki Komobuchi, Hidemitsu Uno, Noboru Ono, Heterocycles, 67, (1) 255 - 267,   2006年01月01日, Benzoporphyrins fused with acenaphthylene or fluoranthene (3) and (4) were prepared by the condensation of bicyclo[2.2.2]octadiene(BCOD)-fused tripyrrane (5) with appropriate pyrrole dialdehydes (13) or (14) and the subsequent retro Diels-Alder reaction. The absorptions of these new porphyrins were very intense at both Soret and Q bands, which might be useful as organic dyes for solar cells. © 2006 The Japan Institute of Heterocyclic Chemistry All rights reserved.
  • Photochemical synthesis of pentacene and its derivatives
    Hiroko Yamada, Yuko Yamashita, Makoto Kikuchi, Hikaru Watanabe, Tetsuo Okujima, Hidemitsu Uno, Hidemitsu Uno, Takuji Ogawa, Keishi Ohara, Noboru Ono, Chemistry - A European Journal, 11, (21) 6212 - 6220,   2005年10月21日, A novel α-diketone precursor of pentacene, 6,13-dihydro-6,13- ethanopentacene-15, 16-dione, was prepared and converted successfully to pentacene in 74% yield by photolysis of the precursor in toluene: Irradiation of the diketone solution in toluene with light of 460 nm under an Ar atmosphere caused the solution to change from yellow to fluore scent orange-pink within a few minutes, after which, purple precipitates appeared. After 35 min, the solution changed to colorless and the purple precipitates were filtered to give pentacene in 74% yield. By contrast, in the presence of oxygen, the color of the solution changed from yellow to pale yellow, and only 6,13-endoperoxide of pentacene was quantitatively obtained. The rate of the reaction upon photolysis was measured by observing the decay of n-π* absorption of the precursor at 460 nm, and was found to be similar in both the presence and absence of oxygen. Therefore, the photoreaction of the α-diketone precursor seemed to occur via the singlet excited state. Because the T-T absorption of pentacene was observed upon photolysis of the precursor in the nanosecond transient absorption measurement under an Ar atmosphere, the excited triplet state of the pentacene generated singlet oxygen by sensitization, and it reacted with the ground-state pentacene to give the 6,13-endoperoxide. The α-diketone deposited on glass was also converted successfully to pentacene film by photoirradiation. In addition, diketone precursors of a mixture of 2,8- and 2,9-dibromopentacene and 2,6-trianthrylene were also prepared and their photocon-version was performed. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Photo precursor for pentacene
    Hidemitsu Uno, Hidemitsu Uno, Yuko Yamashita, Makoto Kikuchi, Hikaru Watanabe, Hiroko Yamada, Tetsuo Okujima, Takuji Ogawa, Takuji Ogawa, Noboru Ono, Tetrahedron Letters, 46, (12) 1981 - 1983,   2005年03月21日, 6,13-Dihydro-6,13-ethanopentacene-15,16-dione gave pentacene efficiently both in solid and in solution by irradiation of light. © 2005 Elsevier Ltd. All rights reserved.
  • An efficient synthesis of conjugation-expanded carba- and azuliporphyrins using a bicyclo[2.2.2]octadiene-fused tripyrrane
    Tetsuo Okujima, Naoki Komobuchi, Yusuke Shimizu, Hidemitsu Uno, Noboru Ono, Tetrahedron Letters, 45, (28) 5461 - 5464,   2004年07月05日, A bicyclo[2.2.2]octadiene-fused tripyrrane was synthesized as a first versatile reagent for the preparation of π-expanded heteroporphyrins. The reaction of the tripyrrane with 1,3-diformylindene and azulene-1,3- dicarbaldehyde afforded the corresponding heteroporphyrins, which were easily converted into tetrabenzocarbaporphyrin and tribenzoazuliporphyrin by retro Diels-Alder reaction. © 2004 Elsevier Ltd. All rights reserved.
  • Efficient preparation of 2-azulenylboronate and Miyaura-Suzuki cross-coupling reaction with aryl bromides for easy access to poly(2-azulenyl)benzenes
    Shunji Ito, Tomomi Terazono, Takahiro Kubo, Tetsuo Okujima, Noboru Morita, Toshihiro Murafuji, Yoshikazu Sugihara, Kunihide Fujimori, Jun Kawakami, Akio Tajiri, Tetrahedron, 60, (25) 5357 - 5366,   2004年06月14日, This paper describes an efficient preparation of 2-azulenylboronate (6) starting from 2-iodoazulene by halogen-metal exchange reaction using n-BuLi and subsequent quenching with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The boronate 6 has been found to undergo Pd-catalyzed Miyaura-Suzuki cross-coupling rea ction with a range of aryl bromides including aromatic poly bromides utilizing Pd 2 (dba) 3 -P(t-Bu) 3 as a catalyst and establishes a strategy to produce novel poly(2-azulenyl)benzenes, some of which are found to be insoluble in common organic solvents, however. The redox behavior of 2-arylazulenes and poly(2-azulenyl)benzenes was examined by cyclic voltammetry (CV) and compared with those of 6-azulenylbenzene derivatives reported previously. © 2004 Elsevier Ltd. All rights reserved.
  • First synthesis of a series of core-modified tetrabenzoporphyrins
    Yusuke Shimizu, Zhen Shen, Tetsuo Okujima, Hidemitsu Uno, Noboru Ono, Chemical Communications, (4) 374 - 375,   2004年02月21日, Successful synthesis of a series of highly conjugated porphyrin analogues, including thia-, dithia- and oxathia-tetrabenzoporphyrins, and their optical properties are reported.
  • Synthesis of 2-aminoazulene derivatives. Nucleophilic and palladium-catalyzed amination of 2-substituted azulene
    Ryuji Yokoyama, Shunji Ito, Tetsuo Okujima, Takahiro Kubo, Masafumi Yasunami, Akio Tajiri, Noboru Morita, Tetrahedron, 59, (41) 8191 - 8198,   2003年10月06日, Amination of 2-substituted azulene was carefully examined using several types of amines, and the scope and limitation of substrates and reagents in these direct nucleophilic aminations were found. The synthesis of 2-aminoazulenes was successfully achieved by the reaction of 2-bromoazulene with several amines via palladium-catalyzed amination. © 2003 Elsevier Ltd. All rights reserved.
  • Reaction of azulenes with 1-trifluoromethanesulfonylpyridinium trifluoromethanesulfonate (TPT) and synthesis of the parent azulene
    Shunji Ito, Ryuji Yokoyama, Tetsuo Okujima, Tomomi Terazono, Takahiro Kubo, Akio Tajiri, Masataka Watanabe, Noboru Morita, Organic and Biomolecular Chemistry, 1, (11) 1947 - 1952,   2003年07月21日, 2-Azulenyl trifluoromethanesulfonate was prepared by the reaction of 2-hydroxyazulene with trifluoromethane-sulfonic anhydride in the presence of triethylamine as a base. Under the use of pyridine, 1-trifluoromethane-sulfonylpyridinium trifluoromethanesulfonate further reacted with 2-azulenyl trifluoromethanesulfonate to give 1-(1-trifluoromethanesulfonyl-1,4-dihydropyridin-4-yl)azulenyl trifluoromethanesulfonate. Moreover, we found that azulenes also reacted with l-trifluoromethanesulfonylpyridinium trifluoromethanesulfonate to give 4-(1-azulenyl)- 1,4-dihydropyridine derivatives and 6-(1-azulenyl)-1-trifluoromethanesulfonyl-1-aza-hexa-1,3.5-triene depending on the reaction conditions. 2-Azulenyl trifluoromethanesulfonate was converted finally into the parent azulene in excellent yield by palladium-catalyzed reduction using formic acid as a reducing reagent.
  • Generation, characterization and some reactions of 1,1-ethylene-1H-azulenium ion
    Mitsunori Oda, Takanori Kajioka, Tetsuo Okujima, Shunji Itoh, Noboru Morita, Ryuta Miyatake, Shigeyasu Kuroda, Chemistry Letters, (10) 1011 - 1012,   1997年12月01日, The title carbocation, generated from 1,1-ethylene-1,6-dihydroazulene and trityl tetrafluoroborate in deuterated acetonitrile at - 20°C, was characterized by means of low temperature NMR spectroscopy, and was found to undergo expansion of the cyclopropane ring at elevated temperature and to react with nucleophiles to give the addition products at the cyclopropane methylene carbon.

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    奥島 鉄雄, 3rd Georgian Bay International Conference on Bioinorganic Chemistry (CanBIC-3),   2011年05月, 招待有り
  • 有機合成化学を活用した塗布変換型有機半導体デバイス
    奥島 鉄雄, 第1回 有機分子・バイオエレクトロニクスの未来を拓く若手研究者討論会,   2010年09月, 招待有り
  • 溶けない分子を溶かして使うには?-有機合成を基盤とした材料開発-
    奥島 鉄雄, 若手研究者のためのセミナー 第26回若手化学者のための化学道場,   2010年09月, 招待有り

特許

  • ジアザポルフィリン化合物又はその塩、半導体材料、膜、電子デバイス、電界効果トランジスタ、及び光電変換素子, 小野 昇・奥島鉄雄・金 光男・山田容子・大坪才華・荒牧晋司・秋山誠治・武井 出・大野 玲・酒井良正, 特願2009-225558, 特開2011-074161
  • ポルフィセン及びその製造法、フィルム、半導体材料、蛍光色素並びに太陽電池, 山田容子・奥島鉄雄・小野 昇・葛原大軌, 特願2008-245760, 特開2010-077054
  • フタロシアニン前駆体及びその製造方法、フタロシアニンの製造方法、並びにフタロシアニン膜の製造方法, 小野 昇・奥島鉄雄・平尾敦子・荒牧晋司・酒井良正, 特願2008-208094, 特開2010-045186
  • 有機顔料前駆体及びそれを用いた有機顔料の製造方法、有機顔料を用いた有機電子素子の製造方法、並びに新規な化合物, 小野 昇・平尾敦子・角井隆功・荒牧晋司・奥島鉄雄・橋本祐介・秋山誠治, 特願2008-032278, 特開2009-215547
  • ビシクロテトラアザポルフィリン化合物及びそれを用いたテトラアザポルフィリン化合物の製造方法、並びに有機電子デバイス及びその製造方法, 小野 昇・奥島鉄雄・菊池 誠・荒牧晋司・酒井良正・平尾敦子, 特願2007-118494, 特開2007-320957
  • ビシクロポルフィリン化合物、ビシクロピロール化合物、化合物の製造方法、有機半導体及びその製造方法, 小野 昇・奥島鉄雄・荒牧晋司, 特願2007-012720, 特開2007-224019

受賞

  •   2014年11月, 有機合成化学協会中国四国支部, 有機合成化学協会中国四国支部奨励賞, 機能性材料を目指した高共役π電子系化合物の合成
  •   2014年04月, 丸山記念研究奨励賞, 機能性有機材料を目指した高共役ポルフィリノイドの創製

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