前駆体法を利用したπ共役拡張芳香族化合物の機能開拓

2015 Fiscal Year Annual Research Report

• Project/Area Number: 25288092
• Research Institution: Nara Institute of Science and Technology
• Principal Investigator: 山田 容子 奈良先端科学技術大学院大学, 物質創成科学研究科, 教授 (20372724)
• Co-Investigator(Kenkyū-buntansha): 葛原 大軌 奈良先端科学技術大学院大学, 物質創成科学研究科, 助教 (00583717) ; 荒谷 直樹 奈良先端科学技術大学院大学, 物質創成科学研究科, 准教授 (60372562)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Keywords: 機能性有機材料 / ペンタセン / TTF / BODIPY / イソインドール / 有機半導体材料 / 発光材料

Outline of Annual Research Achievements

『前駆体法』とは熱や光などの外部刺激による構造変化を利用して、溶解度や不安定性の問題から合成が困難な化合物の合成や、化学構造の変化に伴う物理的性質の大きな変化を，材料の機能変化として利用することを目的とする。本研究はこのような『前駆体法』を駆使して①π系が大きく酸化されやすいアセン系化合物の合成；②溶解度が低いために合成が困難な複素環化合物の新規合成ルートの開拓；③前駆体に光や熱の外部刺激を与えることで発光や半導体特性などの物理特性を発現する潜在性機能材料の開発；に関する合成研究を包括的に行い、機能性材料の開発へと展開することを目的とした。
最終年度である今年度は、p及びn型の有機半導体材料の光変換前駆体・熱変換前駆体の開発、ナノリボンボトムアップ合成のためのユニット開発、ヘテロ原子を含むπ共役拡張分子の開発、ベンゾポルフィリン類縁体の合成を行った。とくに、n型有機半導体はp型に比べて格段に種類が少ないがフラーレン誘導体の光変換前駆体を合成し、その反応性・溶解度などを詳細に検討した。p型材料においては、光変換前駆体法と蒸着法で、同様の電荷移動度と薄膜構造を有する半導体薄膜が得られることを確認した。一方熱変換前駆体法を利用して、ドナーーアクセプター構造により長波長に吸収を有する含窒素化合物の合成を試みたところ、想定外のカップリング反応による二量体を得ることに成功した。またベンゾトリフィリン(2.1.1)は、酸素の２電子還元触媒として働くことがわかった。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Causes of Carryover

27年度が最終年度であるため、記入しない。

Expenditure Plan for Carryover Budget

27年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] National University of Singapore/Nangyang Technological University(Singapore)
  • Country Name: Singapore
  • Counterpart Institution: National University of Singapore/Nangyang Technological University
• [Int'l Joint Research] University of Massatusets(米国)
  • Country Name: U.S.A.
  • Counterpart Institution: University of Massatusets
• [Int'l Joint Research] the Chinese University of Hong Kong(Hong Kong)
  • Country Name: その他の国・地域
  • Counterpart Institution: the Chinese University of Hong Kong
• [Journal Article] Full Characterization and photoelectrochemical behaviors of Pyrene-fused Octaazadecacene and Tetraazaoctacene (2016)
  • Author(s): Z. Wang, J. Miao, G. Long, P. Gu, J. Li, N. Aratani, H. Yamada, B. Liu,* Q. Zhang*
  • Journal Title: Chem. Asian J. Volume: 11 Pages: 482-485
  • DOI: 10.1002/asia.201501276
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Fusing N-heteroacene Analogues into One “Kinked” Molecule with Slipped Two-dimensional Ladder-like Packing (2016)
  • Author(s): J. Zhang, C. Wang, G. Long, N. Aratani, H. Yamada, Q. Zhang*
  • Journal Title: Chem. Sci. Volume: 7 Pages: 1309-1313
  • DOI: 10.1039/C5SC03604F
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Z-Shaped Pentaleno- Acene Dimers with High Stability and Low Band Gap (2016)
  • Author(s): Gaole Dai, Jingjing Chang, Jie Luo, Shaoqiang Dong, Naoki Aratani, Bin Zheng, Kuo-Wei Huang, Hiroko Yamada, and Chunyan Chi
  • Journal Title: Angew, Chem. Int. Ed. Volume: 55 Pages: 2693-2696
  • DOI: 10.1002/anie.201508919
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity (2016)
  • Author(s): Pan Hu, Sangsu Lee, Tun Seng Herng, Naoki Aratani, Théo P. Gonçalves, Qingbiao Qi, Xueliang Shi, Hiroko Yamada, Kuo-Wei Huang, Jun Ding*, Dongho Kim*, and Jishan Wu*
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Pages: 1065-1077
  • DOI: 10.1021/jacs.5b12532
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Laterally p-expanded fluorone dye as an efficient near infrared fluorophore (2016)
  • Author(s): Kyohei Sezukuri, Mitsuharu Suzuki, Hironobu Hayashi, Daiki Kuzuhara, Naoki Aratani*, Hiroko Yamada*
  • Journal Title: Chem. Commun Volume: 52 Pages: 4872-4875
  • DOI: 10.1039/C6CC00237D
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Photoprecursor Approach Enables Preparation of Well-Performing Bulk-Heterojunction Layers Comprising a Highly Aggregating Molecular Semiconductor (2016)
  • Author(s): Mitsuharu Suzuki, Yuji Yamaguchi, Kohei Takahashi, Katsuya Takahira, Tomoyuki Koganezawa, Sadahiro Masuo, Ken-ichi Nakayama*, and Hiroko Yamada*
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 8 Pages: 8644-8651
  • DOI: 10.1021/acsami.6b00345
  • Peer Reviewed
• [Journal Article] Evaluation of Charge Transfer Efficiency of Organic Thin-Film Photovoltaic Devices Fabricated Using Fluorescence Microspectroscopy (2015)
  • Author(s): S. Masuo*, W. Sato, Y. Yamaguchi, M. Suzuki, K. Nakayama, H. Yamada
  • Journal Title: Photochem. Photobiol. Sci. Volume: 14 Pages: 883-889
  • DOI: 10.1039/c4pp00477a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Structure, and Air-stable N-type Field-Effect Transistor Behaviors of Functionalized Octaazanonacene-8,19-dione (2015)
  • Author(s): C. Wang, J. Zhang, G. Long, N. Aratani, H. Yamada, Y. Zhao, Q. Zhang*
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54 Pages: 6292-6296
  • DOI: 10.1002/anie.201500972
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis, Characterization and Memory Performance of Two Organic Small Molecules through Donor-acceptor Design (2015)
  • Author(s): C. Wang, M. Yamashita, B. Hu, Y. Zhou, J. Wang, J. Wu, F. Huo, P. S. Lee, N. Aratani, H. Yamada, Q. Zhang*
  • Journal Title: Asian J. Org. Chem. Volume: 4 Pages: 646-651
  • DOI: 10.1002/ajoc.201500087
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A Tetrabenzoperipentacene Having Stable Five-electron Donating Ability and a Discrete Triple-Layered β-Graphite Form in Crystal (2015)
  • Author(s): A. Matsumoto, M. Suzuki, D. Kuzuhara, H. Hayashi, N. Aratani*, H. Yamada*
  • Journal Title: Angew, Chem. Int. Ed. Volume: 54 Pages: 8175-8178
  • DOI: 10.1002/anie.201502466
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] An electron-deficient tetrathiafulvalene-conjugated bistetracene (2015)
  • Author(s): M. Yamashita, H. Hayashi, N. Aratani*, H. Yamada*
  • Journal Title: Tetrahedron Lett. Volume: 56 Pages: 3804-3808
  • DOI: 10.1016/j.tetlet.2015.04.080
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Evaluation of semiconducting molecular thin films solution-processed via the photoprecursor approach: the case of hexyl-substituted thinoanthracenes (2015)
  • Author(s): C. Quinton, M. Suzuki*, Y. Kaneshige, Y. Tatenaka, C. Katagiri, Y. Yamaguchi, D. Kuzuhara, N. Aratani, K. Nakayama, H. Yamada*
  • Journal Title: J. Mater. Chem.C Volume: 3 Pages: 5995-6005
  • DOI: 10.1039/c5tc00794a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Novel D-p-A Small Molecule with N-heteroacene as Acceptor Moiety for Photovoltaic Application (2015)
  • Author(s): C. Wang, T. Okabe, G. Long, D. Kuzuhara, Y. Zhao, N. Aratani*, H. Yamada,* Q. Zhang*
  • Journal Title: Dyes and Pigments Volume: 122 Pages: 231-237
  • DOI: http://dx.doi.org/10.1016/j.dyepig.2015.06.029
  • Peer Reviewed
• [Journal Article] Indolizino[5,6-b]quinoxaline Derivatives: Intramolecular Charge Transfer Characters and NIR Fluorescence (2015)
  • Author(s): M. Kojima, H. Hayashi, T. Aotake, S. Ikeda, M. Suzuki, N. Aratani, D. Kuzuhara, H. Yamada*
  • Journal Title: Chem. Asian J. Volume: 10 Pages: 2337-2341
  • DOI: dx.doi.org/10.1002/asia.201500597
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Catalytic two­electron reduction of dioxygen catalysed by metal-free [14]triphyrin(2.1.1) (2015)
  • Author(s): K. Mase, K. Ohkubo, Z. Xue, H. Yamada*, S. Fukuzumi*
  • Journal Title: Chem. Sci. Volume: 6 Pages: 6496-6504
  • DOI: 10.1039/C5SC02465J
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Facile synthesis of indolizino[3,4,5-ab]isoindoles by an acid-induced cyclization of 1,2-di(1H-pyrrol-2-yl)benzenes (2015)
  • Author(s): D. Kuzuhara,* S. Miyake, H. Moriyama, Y. Tamura, N. Aratani, H. Yamada*
  • Journal Title: Tetrahedron Lett. Volume: 56 Pages: 4464-5567
  • DOI: doi:10.1016/j.tetlet.2015.08.044
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Charge-Carrier Dynamics in Benzoporphyrin Films Investigated by Time-Resolved THz Spectroscopy (2015)
  • Author(s): K. Ohta, S. Hiraoka, Y. Tamura, H. Yamada, K. Tominaga
  • Journal Title: Appl. Phys. Lett. Volume: 107 Pages: 183302/1-5
  • DOI: 10.1063/1.4934690
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 拡張π共役有機材料の機能開拓と溶液塗布によるデバイス作製プロセスへの応用 (2015)
  • Author(s): 林宏暢、鈴木充朗、葛原大軌、荒谷直樹、山田容子
  • Journal Title: 有機合成化学協会誌 Volume: 73 Pages: 1232-1244
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Photoprecursor approach towards efficient solution-processed organic solar cells (2015)
  • Author(s): Mitsuharu Suzuki, Yuji Yamaguchi, Ken-ichi Nakayama, Hiroko Yamada
  • Organizer: Pacifichem
  • Place of Presentation: Honolulu (USA)
  • Year and Date: 2015-12-15 – 2015-12-20
  • Int'l Joint Research / Invited
• [Presentation] Controlling Vertical Composition Profile in Organic Photovoltaic Active Layers through the Photoprecursor Approach (2015)
  • Author(s): Mitsuharu Suzuki, Yuji Yamaguchi, Ken-ichi Nakayama, Hiroko Yamada
  • Organizer: 2015 MRS Fall Meeting & Exhibit
  • Place of Presentation: Boston (USA)
  • Year and Date: 2015-11-29 – 2015-12-04
  • Int'l Joint Research
• [Presentation] solution-processed organic field-effect transistors of soluble tetrabenzoporphyrins (2015)
  • Author(s): Kotaro Takahashi, Bowen Shan, Xiaomin Xu, Daiki Kuzuhara, Mitsuharu Suzuki, Naoki Aratani, Tomoyuki Koganezawa, Qian Miao, Hiroko Yamada
  • Organizer: 2015 MRS Fall Meeting & Exhibit
  • Place of Presentation: Boston (USA)
  • Year and Date: 2015-11-29 – 2015-12-04
  • Int'l Joint Research
• [Presentation] Precursor Approach for the Preparation of Organic Semiconducting Materials (2015)
  • Author(s): Hiroko Yamada
  • Organizer: 第13回日本-ベルギー高分子科学シンポジウム
  • Place of Presentation: 奈良女子大学（奈良県奈良市）
  • Year and Date: 2015-11-15 – 2015-11-18
  • Int'l Joint Research / Invited
• [Presentation] 溶液プロセスによる積層型有機薄膜太陽電池の開発 (2015)
  • Author(s): 山田容子
  • Organizer: 2015年 日本化学会中国四国支部大会
  • Place of Presentation: 岡山大学 （岡山県岡山市）
  • Year and Date: 2015-11-14 – 2015-11-15
  • Invited
• [Presentation] “前駆体法”による低分子塗布型有機薄膜太陽電池の構築 (2015)
  • Author(s): 山田容子、鈴木充朗、山口裕二、中山健一
  • Organizer: 第６４回高分子科学討論会
  • Place of Presentation: 東北大学（宮城県仙台市）
  • Year and Date: 2015-09-15 – 2015-09-17
  • Invited
• [Presentation] 新しい導電性材料π電子系の科学 (2015)
  • Author(s): 山田 容子
  • Organizer: シーズとニーズの会
  • Place of Presentation: 産業技術総合研究所臨海副都心センター（東京都江東区）
  • Year and Date: 2015-09-02
  • Invited
• [Presentation] Synthesis of Acene for Bandgap Modulated Graphene Nanoribbon (2015)
  • Author(s): Hironobu Hayashi, Hiroko Yamada
  • Organizer: ISNA16 2015
  • Place of Presentation: Madrid (Spain)
  • Year and Date: 2015-07-05 – 2015-07-10
  • Int'l Joint Research
• [Presentation] Synthesis and Physical Properties of a Tetrabenzoperipentacene (2015)
  • Author(s): Akinobu Matsumoto, Mitsuharu Suzuki, Daiki Kuzuhara, Hironobu Hayashi,Naoki Aratani and Hiroko Yamada
  • Organizer: ISNA16 2015
  • Place of Presentation: Madrid (Spain)
  • Year and Date: 2015-07-05 – 2015-07-10
  • Int'l Joint Research
• [Presentation] Photoprecursor approach as an effective means for preparing multilayer organic photovoltaic devices by solution processes (2015)
  • Author(s): H. Yamada, M. Suzuki, Y. Yamaguchi, K. Nakayama
  • Organizer: ICMAT2015
  • Place of Presentation: Singapore
  • Year and Date: 2015-06-28 – 2015-07-03
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of Benzoporphyrin-Diketopyrrolopyrrole Conjugates and Application for Organic Solar Cells (2015)
  • Author(s): D. Kuzuhara, K. Takahashi , N. Yamada, Y. Yamaguchi , M. Suzuki, N. Aratani, K. . Nakayama, H. Yamada
  • Organizer: 227th ECS Meeting
  • Place of Presentation: Chicago (USA)
  • Year and Date: 2015-05-24 – 2015-05-28
  • Int'l Joint Research
• [Presentation] Porphycene-Diketopyrrolopyrrole Conjugates As p-Type Organic Solar Cell Materials (2015)
  • Author(s): D. Kuzuhara, T. Okabe, M. Suzuki, N.i Aratani, H. Yamada
  • Organizer: 227th ECS Meeting
  • Place of Presentation: Chicago (USA)
  • Year and Date: 2015-05-24 – 2015-05-28
  • Int'l Joint Research
• [Patent(Industrial Property Rights)] 有機化合物及びその利用 (2016)
  • Inventor(s): 荒谷直樹、山田容子、青竹達也、井内俊文、山本達也
  • Industrial Property Rights Holder: 荒谷直樹、山田容子、青竹達也、井内俊文、山本達也
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 特願2016-011879
  • Filing Date: 2016-01-25