Synthesis and Properties of Electron Deficient pi-Systems Including Fulvalene as a Key Segment

• Project/Area Number: 24350024
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: MURATA Michihisa 京都大学, 化学研究所, 助教 (30447932)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2014: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2013: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2012: ¥10,790,000 (Direct Cost: ¥8,300,000、Indirect Cost: ¥2,490,000)
• Keywords: 構造有機化学 / PAH / CP-PAH / 固体発光 / エキシマー / 分子間相互作用 / 電子受容性 / 多環芳香族炭化水素 / 単結晶X線構造解析 / 芳香族性 / n型材料 / 有機薄膜太陽電池 / 有機半導体材料 / フラーレン / π共役 / 有機半導体

Outline of Final Research Achievements

Polycyclic aromatic compounds containing fully unsaturated pentagon ring(s) (CP-PAHs) have been intensively studied because of their unique properties such as high electron affinity and reactivity. In this research project, we demonstrated an efficient route for the synthesis of tetrabenzo-fused pyracylene (TBP), which includes both pyracylene and tetracene moieties as key segments. TBP was shown to possess high electron affinity and was found to undergo addition reactions with n-butyllithium or benzyne. These unique reactions allowed us to create 1,4-addition compound or triptycene-type adduct with a curved or planar π-system, respectively. These compounds exhibited distinct emission behaviors in a concentrated solution and solid state.

Research Products

• [Journal Article] Reproducible Fabrication of Highly Efficient Perovskite-based Solar Cells: X-ray Crystallographic Studies on the Formation of CH3NH3PbI3 Layers (2014)
  • Author(s): Wakamiya, A.; Endo, M.; Sasamori, T.; Tokitoh, N.; Ogomi, Y.; Hayase, S.; Murata, Y.
  • Journal Title: Chem. Lett. Volume: 43 Issue: 11 Pages: 711-713
  • DOI: 10.1021/ol501113y
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and Structure of an Open-Cage Thiafullerene C69S: Reactivity Differences of an Open-Cage C70 Tetraketone Relative to Its C60 Analogue. (2014)
  • Author(s): Zhang Rui, Futagoishi Tsukasa, Murata Michihisa, Wakamiya Atsushi, Murata Yasujiro
  • Journal Title: Journal of the American Chemical Society Volume: 136 Issue: 23 Pages: 8193-8196
  • DOI: 10.1021/ja504054s
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Dibenzo[a,f]perylene Bisimide: Effects of Introducing Two Fused Rings (2014)
  • Author(s): Chaolumen; Enno, H.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Journal Title: Chem. Asian J. Volume: 9 Issue: 11 Pages: 3136-3140
  • DOI: 10.1002/asia.201402688
  • Peer Reviewed
• [Journal Article] On-Top π-Stacking of Quasiplanar Molecules in Hole-Transporting Materials: Inducing Anisotropic Carrier Mobility in Amorphous Films. (2014)
  • Author(s): A. Wakamiya, H. Nishimura, T. Fukushima, F. Suzuki, A. Saeki, S. Seki, I. Osaka, T. Sasamori, M. Murata, Y. Murata, H. Kaji
  • Journal Title: Angew. Chem., Int. Ed. Volume: 53 Issue: 23 Pages: 5800-5804
  • DOI: 10.1002/anie.201400068
  • NAID: 120005646482
  • Peer Reviewed
• [Journal Article] Expansion of Orifices of Open C60 Derivatives and Formation of an Open C59S Derivative by Reaction with Sulfur (2013)
  • Author(s): Futagoishi, T.; Murata, M.; Wakamiya, A.; Sasamori, T.; Murata, Y.
  • Journal Title: Org. Lett. Volume: 15 Issue: 11 Pages: 2750-2753
  • DOI: 10.1021/ol401083c
  • Peer Reviewed
• [Journal Article] X-ray observation of a helium atom and placing a nitrogen atom inside He＠C_60 and He＠C_70 (2013)
  • Author(s): 森中裕太
  • Journal Title: Nature Communications Volume: 4 Issue: 1 Pages: 1554-1554
  • DOI: 10.1038/ncomms2574
  • Peer Reviewed
• [Journal Article] Synthesis and photovoltaic properties of acceptor materials based on the dimerization of fullerene C_60 for use in efficient polymer solar cells (2013)
  • Author(s): 森中裕太
  • Journal Title: Chemical Communications Volume: (印刷中) Issue: 35 Pages: 3670-3672
  • DOI: 10.1039/c3cc41084f
  • Peer Reviewed
• [Journal Article] Synthesis and X-Ray Structure of Endohedral Fullerene C60 Dimer Encapsulating a Water Molecule in Each C60 Cage (2013)
  • Author(s): R.Ahang, M. Murata, A. Wakamiya, Y. Murata
  • Journal Title: Chem. Lett. Volume: 42(掲載確定)
  • Peer Reviewed
• [Presentation] 水分子内包アザフラーレンの合成 (2015)
  • Author(s): 橋川祥史、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 日本化学会 第95春季年会 (2015)
  • Place of Presentation: 船橋
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 水単分子ならびに水二量体を内包したフラーレンC70の合成と性質 (2015)
  • Author(s): 張鋭、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 日本化学会 第95春季年会 (2015)
  • Place of Presentation: 船橋
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] ボウル型C60誘導体の小分子内包挙動 (2015)
  • Author(s): 二子石師、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 日本化学会 第95春季年会 (2015)
  • Place of Presentation: 船橋
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Synthesis and Properties of Tetrabenzopyracylene Derivatives (2015)
  • Author(s): Chaolumen; Murata, M.; Sugano, Y.; Wakamiya, A.; Murata, Y.
  • Organizer: 日本化学会 第95春季年会 (2015)
  • Place of Presentation: 船橋
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] π拡張型ピラシレンの合成、性質および反応 (2014)
  • Author(s): 村田理尚、Chaolumen、若宮淳志、村田靖次郎
  • Organizer: 第５回統合物質シンポジウム
  • Place of Presentation: 名古屋
  • Year and Date: 2014-12-19 – 2014-12-20
• [Presentation] 開口部をもつチアフラーレンC69SならびにオキサフラーレンC69O誘導体の合成とX線構造 (2014)
  • Author(s): 張鋭、二子石師、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 第41回有機典型元素化学討論会
  • Place of Presentation: 宇部
  • Year and Date: 2014-11-27 – 2014-11-29
• [Presentation] Development of Synthetic Methods for Endohedral Azafullerenes (2014)
  • Author(s): Hashikawa, Y.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: International Symposium on the Synthesis and Application of Curved Organic Pi-Molecules and Materials
  • Place of Presentation: Uji, Japan
  • Year and Date: 2014-10-19 – 2014-10-21
• [Presentation] Synthesis and X-ray Structure of Open-Cage Thiafullerene C69S and Oxafullerene C69O Derivatives (2014)
  • Author(s): Zhang, R.; Futagoishi, T.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: International Symposium on the Synthesis and Application of Curved Organic Pi-Molecules and Materials
  • Place of Presentation: Uji, Japan
  • Year and Date: 2014-10-19 – 2014-10-21
• [Presentation] Synthesis, Structure, and Properties of Dibenzo[a,f]perylene Bisimide Derivatives (2014)
  • Author(s): Chaolumen; Enno, H.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: International Symposium on the Synthesis and Application of Curved Organic Pi-Molecules and Materials
  • Place of Presentation: Uji, Japan
  • Year and Date: 2014-10-19 – 2014-10-21
• [Presentation] 開口チアフラーレンC69S誘導体の合成とX線構造 (2014)
  • Author(s): 張鋭、二子石師、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 第４回ＣＳＪ化学フェスタ２０１４
  • Place of Presentation: 東京
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] Effects of Dibenzo-Fused Structure at the a and f Bonds in the Perylene Bisimide Skeleton (2014)
  • Author(s): Chaolume; Enno, H.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: 第４回ＣＳＪ化学フェスタ２０１４
  • Place of Presentation: 東京
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] 水素分子内包アザフラーレンの合成 (2014)
  • Author(s): 橋川祥史、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 第４回ＣＳＪ化学フェスタ２０１４
  • Place of Presentation: 東京
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] C69S骨格をもつ開口チアフラーレンの合成とX線構造 (2014)
  • Author(s): 張鋭、二子石師、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 第25回基礎有機化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] Synthesis and Properties of Dibenzo[a,f]perylene Bisimide Derivatives (2014)
  • Author(s): Chaolumen; Enno, H.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: 第25回基礎有機化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] 酸素分子および二酸化炭素分子を内包した開口C60誘導体の合成と性質 (2014)
  • Author(s): 二子石師、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 第25回基礎有機化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] 水素分子を内包したアザフラーレン前駆体の合成 (2014)
  • Author(s): 橋川祥史、村田理尚、若宮淳志、村田靖次郎
  • Organizer: 第25回基礎有機化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] Formation and X-Ray Structure of an Open-cage Thiafullerene C69S (2014)
  • Author(s): Zhang, R.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: The 4th International Conference on MEXT Project of Integtrated Research on Chemical Synthesis
  • Place of Presentation: Uji, Japan
  • Year and Date: 2014-07-10 – 2014-07-11
• [Presentation] Encapsulation of a Hydrogen Molecule inside the Cage of a C59N Precursor (2014)
  • Author(s): Hashikawa, Y.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: The 4th International Conference on MEXT Project of Integtrated Research on Chemical Synthesis
  • Place of Presentation: Uji, Japan
  • Year and Date: 2014-07-10 – 2014-07-11
• [Presentation] Dibenzo[a,f]perylene Bisimide: Effects of the Construction of Tetracene Core (2014)
  • Author(s): Chaolumen; Enno, H.; Murata, M.; Wakamiya, A.; Murata, Y.
  • Organizer: The 4th International Conference on MEXT Project of Integtrated Research on Chemical Synthesis
  • Place of Presentation: Uji, Japan
  • Year and Date: 2014-07-10 – 2014-07-11
• [Presentation] Synthesis and Properties of π-Extended Pyracylenes (2014)
  • Author(s): Michihisa Murata, Yasunori Sugano, Atsushi Wakamiya, and Yasujiro Murata
  • Organizer: The 3rd International Conference on the MEXT Project of Integrated Research on Chemical Synthesis “Synergy of Theory and Molecular Transformation”
  • Place of Presentation: Kyushu University, Fukuoka, Japan
• [Presentation] Synthesis of a Novel Open-cage C60 Derivative with a Ketolactam Moiety (2014)
  • Author(s): Yoshifumi Hashikawa, Michihisa Murata, Atsushi Wakamiya, Yasujiro Murata
  • Organizer: 第46回 フラーレン・ナノチューブ・グラフェン 総合シンポジウム
  • Place of Presentation: 東京大学 伊藤国際学術研究センター 伊藤謝恩ホール
• [Presentation] Tetrabenzopyracylene: Facile Synthesis, Aromaticity, and Electronic Properties (2014)
  • Author(s): Michihisa Murata, Yasunori Sugano, Atsushi Wakamiya, and Yasujiro Murata
  • Organizer: Institute for Chemical Research International Symposium 2014 -The Science and Technology of Smart Materials-
  • Place of Presentation: Obaku Plaza, Kyoto University, Uji, Japan
• [Presentation] X-ray Structure and Reaction of a Precursor for Endohedral C59N (2014)
  • Author(s): Yoshifumi Hashikawa, Michihisa Murata, Atsushi Wakamiya, and Yasujiro Murata
  • Organizer: Institute for Chemical Research International Symposium 2014 -The Science and Technology of Smart Materials-
  • Place of Presentation: Obaku Plaza, Kyoto University, Uji, Japan
• [Presentation] 13 員環C70 誘導体における開口部の構造変換 (2014)
  • Author(s): 張 鋭，村田理尚，若宮淳志，村田 靖次郎
  • Organizer: 日本化学会第94春季年会(2014)
  • Place of Presentation: 名古屋大学 東山キャンパス
• [Presentation] 巨大開口部をもつC60誘導体の合成と小分子内包体のX線構造 (2014)
  • Author(s): 二子石師，村田理尚，若宮淳志，村田靖次郎
  • Organizer: 日本化学会第94春季年会(2014)
  • Place of Presentation: 名古屋大学 東山キャンパス
• [Presentation] 橋川祥史，村田理尚，若宮淳志，村田 靖次郎 (2014)
  • Author(s): フラーレンC60のケトラクタム誘導体における開口部拡大反応
  • Organizer: 日本化学会第94春季年会(2014)
  • Place of Presentation: 名古屋大学 東山キャンパス
• [Presentation] 13員環開口部をもつ水内包C70誘導体の合成と性質 (2013)
  • Author(s): 張鋭, 村田理尚, 村田靖次郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
  • Year and Date: 2013-03-24
• [Presentation] 硫黄挿入を鍵反応としたフラーレンC60への巨大開口部の構築と小分子の内包 (2013)
  • Author(s): 二子石師, 村田理尚, 村田靖次郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
  • Year and Date: 2013-03-24
• [Presentation] ヘリウム原子内包フラーレンの有機合成と新規異種原子内包フラーレンの発生 (2013)
  • Author(s): 森中裕太, 佐藤悟, 若宮厚志, 二川秀史, 溝呂木直美, 田辺史行, 村田理尚, 小松紘一, 古川貢, 加藤立久, 永瀬茂, 赤阪健, 村田靖次郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
  • Year and Date: 2013-03-24
• [Presentation] フラーレンC70における開口部構築と水分子の内包 (2013)
  • Author(s): 張鋭, 村田理尚, 村田靖次郎
  • Organizer: 第44回フラーレン・ナノチューブ・グラフェン総合シンポジウム
  • Place of Presentation: 東京大学伊藤国際学術研究センター謝恩ホール
  • Year and Date: 2013-03-13
• [Presentation] 含硫黄開口部をもつC60誘導体の合成と窒素分子内包体のX線構造 (2013)
  • Author(s): 二子石師, 村田理尚, 村田靖次郎
  • Organizer: 第44回フラーレン・ナノチューブ・グラフェン総合シンポジウム
  • Place of Presentation: 東京大学伊藤国際学術研究センター謝恩ホール
  • Year and Date: 2013-03-12
• [Presentation] ヘリウム内包フラーレンの有機合成ならびに2つの異種原子を内包したフラーレンの発生 (2013)
  • Author(s): 森中裕太, 佐藤悟, 若宮厚志, 二川秀史, 溝呂木直美, 田辺史行, 村田理尚, 小松紘一, 古川貢, 加藤立久, 永瀬茂, 赤阪健, 村田靖次郎
  • Organizer: 第44回フラーレン・ナノチューブ・グラフェン総合シンポジウム
  • Place of Presentation: 東京大学伊藤国際学術研究センター謝恩ホール
  • Year and Date: 2013-03-11
• [Presentation] テトラベンゾピラシレン：合成，芳香族性および性質 (2013)
  • Author(s): 村田理尚，菅野泰功，若宮淳志，村田靖次郎
  • Organizer: 統合物質創製化学推進事業 第４回若手研究会
  • Place of Presentation: 名古屋クラウンホテル
• [Presentation] Tetrabenzopyracylene: Facile Synthesis, Aromaticity, Solid State Structures, and Electronic Properties (2013)
  • Author(s): Michihisa Murata, Yasunori Sugano, Atsushi Wakamiya, and Yasujiro Murata
  • Organizer: 15th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Taipei, Taiwan
• [Presentation] Synthesis and Reactions of Novel Endohedral Fullerenes (2013)
  • Author(s): Yasujiro Murata, Yuta Morinaka, Tsukasa Futagoishi, Rui Zhang, Michihisa Murata, Atsushi Wakamiya
  • Organizer: 15th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Taipei, Taiwan
• [Presentation] Synthesis and X-Ray Structure of Endohedral Fullerene C60 Dimer Encapsulating H2O in Each C60 Cage (2013)
  • Author(s): Rui Zhang, Michihisa Murata, Atsushi Wakamiya, and Yasujiro Murata
  • Organizer: 15th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Taipei, Taiwan
• [Presentation] Orifice Expansion of Open C60 and Formation of an Open C59S by Reaction with Sulfur (2013)
  • Author(s): Tsukasa Futagoishi, Michihisa Murata, Atsushi Wakamiya, Takahiro Sasamori, and Yasujiro Murata
  • Organizer: 15th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Taipei, Taiwan
• [Presentation] H2O@C60の固体反応ならびに[2+2]型二量体のＸ線構造 (2013)
  • Author(s): Rui Zhang, Michihisa Murata, Atsushi Wakamiya, Yasujiro Murata
  • Organizer: 第45回フラーレン・ナノチューブ・グラフェン総合シンポジウム
  • Place of Presentation: 大阪大学
• [Presentation] 硫黄挿入反応を利用した新規開口C60誘導体の合成と小分子内包体のX線構造 (2013)
  • Author(s): 二子石師，村田理尚，若宮淳志，村田靖次郎
  • Organizer: 第24回基礎有機化学討論会
  • Place of Presentation: 学習院大学目白キャンパス
• [Presentation] 水分子を内包したダンベル型C60ダイマーの合成と構造 (2013)
  • Author(s): 張 鋭，村田理尚，若宮淳志，村田靖次郎
  • Organizer: 第24回基礎有機化学討論会
  • Place of Presentation: 学習院大学目白キャンパス
• [Presentation] 巨大な開口部をもつ開口フラーレン誘導体の合成とN2内包体のX線構造 (2013)
  • Author(s): 二子石師，村田理尚，若宮淳志，村田靖次郎
  • Organizer: 第９回有機元素化学セミナー
  • Place of Presentation: 京都大学宇治キャンパスきはだホール
• [Presentation] 水内包フラーレンC60の二量化とX線構造 (2013)
  • Author(s): 張 鋭，村田理尚，若宮淳志，村田靖次郎
  • Organizer: 第９回有機元素化学セミナー
  • Place of Presentation: 京都大学宇治キャンパスきはだホール
• [Presentation] ダンベル型フラーレン誘導体の合成と光電変換特性 (2012)
  • Author(s): 村田理尚, 登政博, 若宮淳志, 佐川尚, 吉川暹, 村田靖次郎
  • Organizer: 日本学術振興会産学協力研究会 第9回「次世代の太陽光発電システム」シンポジウム
  • Place of Presentation: 京都テルサ
  • Year and Date: 2012-05-31
• [Presentation] Synthesis and Photophysical Properties of Azafullerenes Directly Connected to an Organic Dye (2012)
  • Author(s): Yasujiro Murata, Michihisa Murata, Satoshi Katsuya, Kei Ohkubo, Shunichi Fukuzumi
  • Organizer: 4th International Symposium on Emergence of Highly Elaborated Pi-Space and Its Function
  • Place of Presentation: Hamanako Royal Hotel
• [Presentation] Synthesis and Photovoltaic Properties of Dumbbell-Shaped Fullerene Derivatives (2012)
  • Author(s): Michihisa Murata, Masahiro Nobori, Yuta Morinaka, Atsushi Wakamiya, Takashi Sagawa, Susumu Yoshikawa, Yasujiro Murata
  • Organizer: Tne Twelfth International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: Rihga Royal Hotel Kyoto
• [Presentation] ダンベル型フラーレン誘導体 : 有機薄膜太陽電池のモルフォロジー制御 (2012)
  • Author(s): 村田理尚, 登政博, 森中裕太, 若宮淳志, 佐川尚, 吉川暹, 村田靖次郎
  • Organizer: 第23回基礎有機化学討論会
  • Place of Presentation: 京都テルサ
• [Presentation] Dumbbell-Shaped Fullerenes : Tuning the Morphology of the Active Layer in Bulk-Heterojunction Solar Cells (2012)
  • Author(s): Michihisa Murata
  • Organizer: 3rd International Symposium of Advanced Energy Science -Toward Zero-Emission Energy-
  • Place of Presentation: Kihada Hall, Obaku Flaza, Kyoto University Uji Campus
• [Presentation] 17員環開口部をもつ新規フラーレン誘導体の合成と性質 (2012)
  • Author(s): 村田靖次郎, 桜井悠子, 二子石師, 村田理尚, 黒飛敬, 若宮淳志
  • Organizer: 新学術領域研究「高次π空間の創発と機能開発」第8回公開シンポジウム
  • Place of Presentation: ホテルアローレ, 加賀, 金沢
• [Presentation] Synthesis and Photophysical Properties of Azafullerenes Directly Connected to an Organic Dye (2012)
  • Author(s): Michihisa Murata, Satoshi Katsuya, Yasujiro Marata, Kei Ohkubo, Shunichi Fukuzumi
  • Organizer: Tne 10th International Conference on Heteroatom Chemistry (ICHAC-10)
  • Place of Presentation: Obaku Plaza, Kyoto University
• [Book] Organic Synthesis of Endohedral Fullerenes Encapsulating Helium, Dihydrogen, and Water., In Organic Nanomaterials, T. Torres, G. Bottari, Eds. (2013)
  • Author(s): M. Murata, Y. Murata, K. Komatsu
  • Publisher: Wiley-Blackwell