Construction of Highly Conjugated Compounds Based on the Pericyclic Cycloreversion

2010 Fiscal Year Final Research Report

• Project/Area Number: 20550047
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Ehime University
• Principal Investigator: UNO Hidemitsu Ehime University, 大学院・理工学研究科, 教授 (20168735)
• Research Collaborator: YAMADA Hiroko 奈良先端科学技術大学院, 准教授 (20372724) ; OKUJIMA Tetsuo 愛媛大学, 大学院・理工学研究科, 准教授 (60359924) ; KOBAYASHI Nagao 東北大学, 大学院・理学研究科, 教授 (60124575) ; MORI Shigeki 愛媛大学, 総合科学研究支援センター, 助教 (30572028) ; KIM DongHo Yonsei University, Korea, Professor
• Project Period (FY): 2008 – 2010
• Keywords: 構造有機化学 / 有機電子材料

Research Abstract

I have explored the methodology for synthesis of highly conjugated compounds applying the pericyclic cycloreversion of the precursors in the final step such as thermal retro-Diels-Alder reaction and photo de-thiocarbonylation. These precursors are easily purified due to high solubility toward common solvents and high stability toward oxidation. The targeted highly conjugated compounds can be obtained in a highly pure form by the thorough purification of the precursors. I have developed this methodology, prepared the π-fused compounds, and then clarified their intrinsic properties.

Research Products

• [Journal Article] Cyclo[8]isoindoles : Ring-Expanded and Annelated Porphyrinoids (2011)
  • Author(s): T.Okujima, G.Jin, N.Matsumoto, J.Mack, S.Mori, K.Ohara, D.Kuzuhara, C.Ando, N.Ono, H.Yamada, H.Uno, N.Kobayashi
  • Journal Title: Angew.Chem.Int.Ed. in press Pages: DOI:10.1002/anie.201007510.
• [Journal Article] Synthesis of π-Expanded O-Chelated Boron-Dipyrromethene As an NIR Dye (2011)
  • Author(s): Y.Tomimori, T.Okujima, T.Yano, S.Mori, N.Ono, H.Yamada, H.Uno
  • Journal Title: Tetrahedron 67 Pages: 3187-3193
• [Journal Article] Ultrafast Intramolecular Energy Relaxation Dynamics of Benzoporphyrins : Influence of Fused Benzo Rings on Singlet Exited States (2011)
  • Author(s): P.Kim, J.Sung, H.Uoyama, T.Okujima, H.Uno, D.Kim
  • Journal Title: J.Phys.Chem.B 115 Pages: 3784-3792
• [Journal Article] Synthesis, Properties, and Ambipolar Organic Field-Effect Transistor Performances of Symmetrically Cyanated Pentacene and Naphthacene as Air-Stable Acene Derivatives (2011)
  • Author(s): S.Katsuta, D.Miyagi, H.Yamada, T.Okujima, S.Mori, K.Nakayama, H.Uno
  • Journal Title: Org.Lett. 13 Pages: 1454-1457
• [Journal Article] First Synthesis of Dodecasubstituted Porphycenes (2011)
  • Author(s): D.Kuzuhara, H.Yamada, K.Yano, T.Okujima, S.Mori, H.Uno
  • Journal Title: Chem.Eur.J. 17 Pages: 3376-3383
• [Journal Article] Photophysical insights into supramolecular interaction of a designed bisporphyrin with fullerenes C_<60> and C_<70> (2011)
  • Author(s): D.Pal, M.Furukawa, N.Komatsu, H.Uno, S.Bhattacharya
  • Journal Title: Spectrochim.Acta A 78 Pages: 185-190
• [Journal Article] New synthesis of meso-free-[14]triphyrin (2.1.1) by McMurry coupling and its derivatization to Mn (I) and Re (I) complexes (2011)
  • Author(s): D.Kuzuhara, H.Yamada, Z.-L.Xue, T.Okujima, S.Mori, Z.Shen, H.Uno
  • Journal Title: Chem.Commun. 47 Pages: 722-724
• [Journal Article] Synthesis and properties of BCOD-fused trithiasapphyrin and trithiabenzosapphyrins (2010)
  • Author(s): T.Okujima, T.Kikkawa, S.Kawakami, Y.Shimizu, H.Yamada, N.Ono, H.Uno
  • Journal Title: Tetrahedron 66 Pages: 7213-7218
• [Journal Article] Synthesis of π-expanded BODIPYs and their fluorescent properties in the visible-near-infrared region (2010)
  • Author(s): T.Okujima, Y.Tomimori, J.Nakamura, H.Yamada, H.Uno, N.Ono
  • Journal Title: Tetrahedron 66 Pages: 6895-6900
• [Journal Article] Pentacene precursors for solutionprocessed OFETs (2010)
  • Author(s): H.Uoyama, H.Yamada, T.Okujima, H.Uno
  • Journal Title: Tetrahedron 66 Pages: 6889-6894
• [Journal Article] Synthesis, Crystal Structure, and Photodynamics of π-Expanded Porphyrin-Fullerene Dyads Synthesized by Diels-Alder Reaction (2010)
  • Author(s): H.Yamada, K.Ohkubo, D.Kuzuhara, T.Takahashi, A.S.D.Sandanayaka, T.Okujima, K.Ohara, O.Ito, H.Uno, N.Ono, S.Fukuzumi, J.Phys.
  • Journal Title: Chem.B 114 Pages: 14717-14728
• [Journal Article] Synthesis of 2,3-dihydrobenzo[1,4]dithiinfused porphyrins (2010)
  • Author(s): G.Jin, T.Okujima, Y.Hashimoto, H.Yamada, H.Uno, N.Ono
  • Journal Title: Phosphorus, Sulfur Silicon Relat.Elem. 185 Pages: 1108-1116
• [Journal Article] Highly Pure Synthesis, Spectral Assignments, and Two-Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units (2010)
  • Author(s): H.Uoyama, K.S.Kim, K.Kuroki, J.-Y.Shin, T.Nagata, T.Okujima, H.Yamada, N.Ono, D.Kim, H.Uno
  • Journal Title: Chem.Eur.J. 16 Pages: 4063-4074
• [Journal Article] Synthesis and photochemical properties of π-diks precursors for π-expanded porphyrins etoporphyrins as precursors for π-expanded porphyrins (2010)
  • Author(s): H.Yamada, D.Kuzuhara, K.Ohkubo, T.Takahashi, T.Okujima, H.Uno, N.Ono, S.Fukuzumi
  • Journal Title: J.Mater.Chem. 20 Pages: 3011-3024
• [Journal Article] Preparation of highly conjugated oligoaza-PAHs based on the oxidative intramolecular coupling of bicyclo[2.2.2]-octadiene-fused pyrrole (2010)
  • Author(s): H.Uno, T.Takiue, H.Uoyama, T.Okujima, H.Yamada, G.Masuda
  • Journal Title: Heterocycles 82 Pages: 791-802
• [Journal Article] Synthesis of Tetrabenzoporphyrins Fused with Fluoranthenes (2010)
  • Author(s): J.Nakamura, T.Okujima, Y.Tomimori, N.Komobuchi, H.Yamada, H.Uno, N.Ono
  • Journal Title: Heterocycles 80 Pages: 1165-1175
• [Journal Article] Thermal Behabior of Bicyclo[2.2.2]-octadiene-Installed Precursors for 2H-Anthra[2,3-c]pyrroles and Anthra-[2,3-c]thiophene (2010)
  • Author(s): H.Uoyama, C.Chenxin, H.Tahara, Y.Shimizu, H.Hagiwara, Y.Hanasaki, H.Yamada, T.Okujima, H.Uno
  • Journal Title: Heterocycles 80 Pages: 1187-1196
• [Journal Article] Photochemical Synthesis of Tetraarylsubstituted Pentacenes (2010)
  • Author(s): S.Katsuta, H.Yamada, T.Okujima, H.Uno
  • Journal Title: Tetrahedron Lett. 51 Pages: 1397-1400
• [Journal Article] First Synthesis of meso-Chlorinated Tetrabenzoporphyrins (2009)
  • Author(s): S.Ito, L.T.Phong, T.Komatsu, N.Igarashi, S.Otsubo, Y.Sakai, A.Ohno, S.Aramaki, Y.Tanaka, H.Uno, T.Oba, K.Hiratani
  • Journal Title: Eur.J.Org.Chem. Pages: 5373-5382
• [Journal Article] First Synthesis of Porphyrin-Fused 1,10-Phenanthroline-Ruthenium (II) Complexes (2009)
  • Author(s): T.Okujima, A.Mifuji, J.Nakamura, H.Yamada, H.Uno, N.Ono
  • Journal Title: Org.Lett. 11 Pages: 4088-4091
• [Journal Article] 1-Aminoisoindole as a useful π-system elongation unit (2009)
  • Author(s): T.Akiyama, H.Uoyama, T.Okujima, H.Yamada, N.Ono, H.Uno
  • Journal Title: Tetrahedron 65 Pages: 4345-4350
• [Journal Article] Organic Thin-Film Transistor from a Pentacene Photo Precursor (2009)
  • Author(s): A.Masumoto, Y.Yamashita, S.Go, T.Kikuchi, H.Yamada, T.Okujima, N.Ono, H.Uno
  • Journal Title: Jpn.J.Appl.Phys. Pages: 051505/1-5
• [Journal Article] Synthesis, structures, and properties of BCOD-fused porphyrins and benzoporphyrins (2009)
  • Author(s): H.Uoyama, T.Takiue, K.Tominaga, N.Ono, H.Uno
  • Journal Title: J.Porphyrins Phthalocyanines 13 Pages: 122-135
• [Journal Article] Synthesis and properties of benzene-fused diporphyrins with various metals (2009)
  • Author(s): H.Uno, M.Hashimoto, A.Fujimoto
  • Journal Title: Heterocycles 77 Pages: 887-898
• [Journal Article] Soluble precursors of 2,3-naphthalocyanine and phthalocyanine for use in thin film transistors (2008)
  • Author(s): A.Hirao, T.Akiyama, T.Okujima, H.Yamada, H.Uno, Y.Sakai, S.Aramaki, N.Ono
  • Journal Title: Chem.Commun. Pages: 4714-4716
• [Journal Article] Preparation of 1,3,3a,7a-tetrahydroisothia-naphthene and its application to tetrahydrothiophene-fused porphyrin (2008)
  • Author(s): Y.Katsuyama, E.Yoshida, H.Uoyama, N.Ono, H.Uno
  • Journal Title: Heterocycles 76 Pages: 667-678
• [Journal Article] Synthesis and Characterization of Tetraanthroporphyrins (2008)
  • Author(s): H.Yamada, D.Kuzuhara, T.Takahashi, Y.Shimizu, K.Uota, T.Okujima, H.Uno, N.Ono
  • Journal Title: Org.Lett. 10 Pages: 2947-2950
• [Journal Article] Selective synthesis of 5-alkenyl-15-alkynyl-porphyrin and 5,15-dialkynylporphyrin by 2+2 acid-catalyzed condensation of dipyrrylmethane and TMS propynal (2008)
  • Author(s): H.Yamada, K.Kushibe, S.Mitsuogi, T.Okujima, H.Uno, N.Ono
  • Journal Title: Tetrahedron Lett. 49 Pages: 4731-4733
• [Journal Article] Application of MCD Spectroscopy and TD-DFT to Nonplanar Core-Modified Tetrabenzoporphyrins : Effect of ReducedSymmetry on Nonplanar Porphyrinoids (2008)
  • Author(s): J.Mack, M.Bunya, Y.Shimizu, H.Uoyama, N.Komobuchi, T.Okujima, H.Uno, S.Ito, M.J.Stillman, N.Ono, N.Kobayashi
  • Journal Title: Chem.Eur.J. 14 Pages: 5001-5020
• [Journal Article] Photophysical properties of a novel Ni(II)-diporphyrin in presence of fullerenes : Insights from experimental and theoretical studies (2008)
  • Author(s): S.Bhattacharya, M.Hashimoto, A.Fujimoto, T.Kimura, H.Uno, N.Komatsu
  • Journal Title: Spectrochim.Acta, Part A 70A Pages: 416-424
• [Journal Article] Synthesis of extremely soluble precursors of tetrabenzoporphyrins (2008)
  • Author(s): T.Okujima, Y.Hashimoto, G.Jin, H.Yamada, H.Uno, N.Ono
  • Journal Title: Tetrahedron 64 Pages: 2405-2411
• [Journal Article] Thermal behavior of free-base and core-modified bicyclo [2.2.2] octadienefused porphyrins (2008)
  • Author(s): H.Uno, Y.Shimizu, H.Uoyama, Y.Tanaka, T.Okujima, N.Ono
  • Journal Title: Eur.J.Org.Chem. Pages: 87-98
• [Presentation] ベンゾ[1,2-c;4,5-c']ジピロール前駆体の合成とその反応 (2011)
  • Author(s): 田原寛之、山上薫、桑島未紀、奥島鉄雄、森重樹、山田容子、宇野英満
  • Organizer: 日本化学会第91春季年会(震災により講演中止)
  • Year and Date: 20110300
• [Presentation] ベンゼン架橋オリゴポルフィリンの合成と物性 (2011)
  • Author(s): 魚山大樹、奥島鉄雄、山田容子、宇野英満
  • Organizer: 日本化学会第91春季年会(震災により講演中止)
  • Year and Date: 20110300
• [Presentation] β位で縮環したbisBODIPYの合成と物性 (2011)
  • Author(s): 中村光則、田原寛之、魚山大樹、奥島鉄雄、山田容子、森重樹、宇野英満
  • Organizer: 日本化学会第91春季年会(震災により講演中止)
  • Year and Date: 20110300
• [Presentation] Synthesis and properties of π-fused core-modified porphyrin oligomers (2010)
  • Author(s): H.Watanabe, H.Uoyama, S.Mori, T.Okujima, H.Yamada, H.Uno
  • Place of Presentation: Honolulu, USA.
  • Year and Date: 2010-12-17
• [Presentation] Synthesis and properties of bicyclo[2.2.2]-octadiene-connected hexaphyrin (2010)
  • Author(s): S.Mori, H.Uoyama, T.Takiue, H.Uno
  • Place of Presentation: Honolulu, USA.
  • Year and Date: 2010-12-17
• [Presentation] ビシクロ[2.2.2]オクタジエン架橋ジピロールを用いた新規ポルフィリノイドの探索 (2010)
  • Author(s): 田原寛之・魚山大樹、奥島鉄雄、森重樹、山田容子、宇野英満
  • Organizer: 第40回複素環化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2010-10-19
• [Presentation] Synthesis of Porphyrinoids with Novel π-System from BCOD-connected Dipyrrole (2010)
  • Author(s): 宇野英満
  • Place of Presentation: New Mexico, USA.
  • Year and Date: 2010-07-08
• [Presentation] ビシクロ[2.2.2]オクタジエン環を組み込んだポルフィリノイドの合成と物性 (2010)
  • Author(s): 田原寛之、魚山大樹、山田容子、奥島鉄雄、森重樹、宇野英満
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
  • Year and Date: 2010-03-27
• [Presentation] Synthesis of Diethanoacene-fused Diporphyrins and their Complex Formation with Fullerenes (2009)
  • Author(s): M.Furukawa, S.Bhattacharya, N.Komatsu, H.Uno
  • Organizer: IKCOC-11
  • Place of Presentation: Kyoto
  • Year and Date: 2009-11-12
• [Presentation] テトラブロモ-o-キシレンを用いたアンスラ[2,3-c]ヘテロ五員環前駆体の合成 (2009)
  • Author(s): 田原寛之、魚山大樹、小野昇、奥島鉄雄、山田容子、宇野英満
  • Organizer: 日本化学会西日本大会
  • Place of Presentation: 松山
  • Year and Date: 2009-11-08
• [Presentation] ビシクロ[2.2.1]ヘプタジエン-7-オンのキレトロピー反応を用いた新規π電子系化合物の合成 (2009)
  • Author(s): 桑島未紀、垣谷兆政、山田容子、奥島鉄雄、宇野英満
  • Organizer: 日本化学会西日本大会
  • Place of Presentation: 松山
  • Year and Date: 2009-11-08
• [Presentation] 溶液法を用いた有機薄膜トランジスタ作成のためのペンタセン前駆体の熱及び光変換の研究 (2009)
  • Author(s): 魚山大樹、永田央、奥島鉄雄、山田容子、宇野英満
  • Organizer: 日本化学会西日本大会
  • Place of Presentation: 松山
  • Year and Date: 2009-11-08
• [Presentation] ベンゼン架橋十字型ポルフィリン5量体の合成と物性 (2009)
  • Author(s): 魚山大樹、永田央、奥島鉄雄、山田容子、宇野英満
  • Organizer: 日本化学会西日本大会
  • Place of Presentation: 松山
  • Year and Date: 2009-11-07
• [Presentation] Complex Formation of Diethanoacenebridged Diporphyrins with Fullerenes (2009)
  • Author(s): M.Furukawa, M.Hashimoto, S.Bhattacharya, N.Komatsu, H.Uno
  • Place of Presentation: Luxembourg.
  • Year and Date: 2009-07-11
• [Presentation] ビシクロ[2.2.2]オクタジエンを内部に架橋したヘキサフィリンの合成 (2009)
  • Author(s): 魚山大樹、滝上貴大、宇野英満
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-29
• [Presentation] 7-t-ブトキシビシクロ[2.2.1]オクタジエンが縮環したピロールの合成と反応 (2009)
  • Author(s): 宇野英満、魚山大樹、垣谷兆政
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-28
• [Presentation] ジエタノアセン融合ジポルフィリンとフラーレンとの錯形成 (2009)
  • Author(s): 古川美奈、橋本昌和、小松直樹、宇野英満
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-27
• [Presentation] ビシクロ[2.2.2]オクタジエンおよびベンゼン縮合オリゴポルフィリンの構造と物性 (2008)
  • Author(s): 魚山大樹、宇野英満
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 福山
  • Year and Date: 2008-11-21
• [Presentation] 分子認識ツールを指向したジエタノアントラセン融合ジポルフィリンの合成研究 (2008)
  • Author(s): 橋本昌和、宇野英満
  • Organizer: 第38回複素環化学討論会
  • Place of Presentation: 福山
  • Year and Date: 2008-11-21
• [Presentation] Bicyclo[2.2.2]octadiene-fused Porphyrins. Structures, Properties, and Reactivities (2008)
  • Author(s): 宇野英満
  • Organizer: 5th Inernational Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Moscow, Russia.
  • Year and Date: 2008-07-06
• [Remarks] ホームページ等
  • URL: http://chem.sci.ehime-u.ac.jp/~orgchem1/
• [Patent(Industrial Property Rights)] アセンジイミド化合物の製造法 (2011)
  • Inventor(s): 宇野英満、山田容子、勝田修平、田中和樹
  • Industrial Property Rights Holder: 愛媛大学
  • Industrial Property Number: 特許,特願2011-48301
  • Filing Date: 20110000
• [Patent(Industrial Property Rights)] 高共役化合物及びその前駆体、並びに高共役化合物の製造法 (2010)
  • Inventor(s): 宇野英満、増田豪
  • Industrial Property Rights Holder: 愛媛大学、日本触媒
  • Industrial Property Number: 特許,特願2010-28231
  • Filing Date: 20100000
• [Patent(Industrial Property Rights)] 含ハロゲン-1,3-ジホルミル-2-ベンゾチオフェン、含ハロゲンチアポルフィリンおよびこれらの製造方法 (2009)
  • Inventor(s): 宇野英満、増田豪
  • Industrial Property Rights Holder: 愛媛大学、日本触媒
  • Patent Publication Number: 特許特開2009-023931
  • Filing Date: 20090000
• [Patent(Industrial Property Rights)] 含ハロゲンベンゾポルフィリンおよびその錯体、並びに含ハロゲンベンゾポルフィリンの製造方法 (2009)
  • Inventor(s): 宇野英満、増田豪
  • Industrial Property Rights Holder: 愛媛大学、日本触媒
  • Patent Publication Number: 特許,特開2009-062356
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• [Patent(Industrial Property Rights)] 新規化合物および有機半導体素子の製造方法 (2009)
  • Inventor(s): 桝本茜、菊池憲裕、小野昇、宇野英満、中島容子
  • Industrial Property Rights Holder: キヤノン
  • Patent Publication Number: 特許,特開2009-081408
  • Filing Date: 20090000
• [Patent(Industrial Property Rights)] Isoindoles, compounds prepared from the same, and processes for production of both (2008)
  • Inventor(s): 宇野英満, 増田豪, T.Iida
  • Industrial Property Rights Holder: 愛媛大学、日本触媒
  • Industrial Property Number: 特許,WO 2008016085
  • Filing Date: 20080000
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• [Patent(Industrial Property Rights)] Novel organic precursor compound and method of producing organic semiconductor device (2008)
  • Inventor(s): A.Masumoto, 中島容子 菊池憲, 宇野英満, 小野昇
  • Industrial Property Rights Holder: キヤノン
  • Industrial Property Number: 特許,US 2008171403
  • Filing Date: 20080000
  • Overseas