3回対称π電子系による非相互貫入ヘキサゴナルネットの造形と構造・物性ダイナミズム

• Project Area: pi-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions
• Project/Area Number: 15H00998
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Osaka University
• Principal Investigator: 久木 一朗 大阪大学, 工学研究科, 助教 (90419466)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2016: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2015: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 水素結合 / 有機構造体 / 3回対称性 / ヘキサゴナルネットワーク / 多孔質材料 / カルボン酸 / デヒドロアヌレン / 結晶工学 / π造形 / 2次元ネットワーク / 多孔質構造 / 有機結晶 / π造形科学 / 超分子化学 / パイ共役 / 層構造

Outline of Annual Research Achievements

3回対称性の分子あるいは超分子シントンから形成される水素結合性の多孔性2次元ヘキサゴナルネットワーク(H-HexNet)を相互貫入なしに積層化できれば、化学種の吸着・貯蔵材や、超分子集合体を構築する足場材としても展開できる。我々は、分子自身が空孔をもったC3対称性π共役環状分子にo-ターフェニルジカルボン酸部位を導入した環状π電子系T18が、水素結合によって複数種の大きな包接空間をもったH-HexNetを形成し、それらが相互貫入なく積層した低密度H-HexNet積層構造を与えることを見出した。さらに本手法を大きさの異なる一連のパイ電子系に適応することによって、本手法の一般化と多様なH-HexNet積層体の構築および機能化について検討した。
DMFと芳香族分子の混合溶媒から50~100度で結晶化することによってすべての系でH-HexNet積層構造の単結晶を得た。H-NexNetはいずれも相互貫入なく積層しているが、積層様式(層のずれ具合)はそれぞれの共役コアの構造に依存する。網目状の空間には, 再結晶に用いた芳香族分子が包接されており, その包接空間の体積比は４１～５９％である。これらの積層構造の空隙部に包接された溶媒分子を除去したところ、２つの構造体では依然として高い結晶性を保持しており、ガス吸着実験から多孔性を維持していることが分かった。粉末Ｘ線解析および計算化学を用いた結晶構造予測法によって活性化後の結晶構造を同定・推定した。いずれの場合も層のずれによってH-NexNet骨格が大きく重なり、直径8.5~8.9 Åの1次元チャネル空間が形成されている。この空孔への低級炭化水素の吸着挙動および、この空間を足場としたC60の配列についても明らかにした。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Universidad de Castilla-La Mancha(Spain)
• [Int'l Joint Research] NCNST(China)
• [Journal Article] Precise Elucidations on Stacking Manners of Hydrogen-Bonded Two-Dimensional Organic Frameworks Composed of X-Shaped π-Conjugated Systems (2017)
  • Author(s): Ichiro Hisaki, Nur Qadya Emilya Affendy, Norimitsu Tohnai
  • Journal Title: CrystEngComm Volume: 印刷中 Issue: 33 Pages: 4892-4898
  • DOI: 10.1039/c7ce00183e
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Fluoreno[2,3-b]fluorene vs Indeno[2,1-b]fluorene: Unusual Relationship between the Number of π Electrons and Excitation Energy in m-Quinodimethane-Type Singlet Diradicaloids (2017)
  • Author(s): Hirokazu Miyoshi, Masahito Miki, Shintaro Hirano, Akihiro Shimizu, Ryohei Kishi, Kotaro Fukuda, Daisuke Shiomi, Kazunobu Sato, Takeji Takui, Ichiro Hisaki, Masayoshi Nakano, Yoshito Tobe
  • Journal Title: J. Org. Chem. Volume: 82 Issue: 3 Pages: 1380-1388
  • DOI: 10.1021/acs.joc.6b02500
  • Peer Reviewed
• [Journal Article] Synthesis of bright red-emissive dicyanoethenobridged hexa-peri-hexabenzocoronene dimers (2017)
  • Author(s): Kazuma Oda, Satoru Hiroto, Ichiro Hisaki, Hiroshi Shinokubo
  • Journal Title: Org. Biomol. Chem. Volume: 15 Issue: 6 Pages: 1426-1434
  • DOI: 10.1039/c6ob02775j
  • NAID: 120006305604
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A New Strategy to Construct Functional Porous Crystals by Mixed Crystallization through Charge Transfer Interaction (2017)
  • Author(s): Tetsuya Miyano, Ichiro Hisaki, Norimitsu Tohnai
  • Journal Title: Chem. Lett. Volume: 46 Issue: 2 Pages: 225-227
  • DOI: 10.1246/cl.160947
  • NAID: 130005317099
  • Peer Reviewed
• [Journal Article] Stacked Antiaromatic Porphyrins (2016)
  • Author(s): Ryo Nozawa, Hiroko Tanaka, Won-Young Cha, Yongseok Hong, Ichiro Hisaki, Soji Shimizu, Ji-Young Shin, Tim Kowalczyk, Stephan Irle, Dongho Kim, Hiroshi Shinokubo
  • Journal Title: Nature Commun. Volume: 7 Pages: 13620-13620
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hierarchical Construction of SHG-active Polar Crystals by Using Multi-component Crystals (2016)
  • Author(s): Tetsuya Miyano, Tatsuya Sakai, Ichiro Hisaki, Hideki Ichida, Yasuo Kanematsu, Norimitsu Tohnai
  • Journal Title: Chem. Commun. Volume: 52 Issue: 94 Pages: 13710-13713
  • DOI: 10.1039/c6cc07544d
  • Peer Reviewed
• [Journal Article] Synthesis of Hexagonal Shape-Persistent Cyclophane with D2h Symmetry (2016)
  • Author(s): Kazunari Tagawa, Shigeki Mori, Masayoshi Takase, Tetsuo Okujima, Ichiro Hisaki, Hidemitsu Uno
  • Journal Title: Tetrahedron Lett. Volume: 57 Issue: 36 Pages: 4079-4081
  • DOI: 10.1016/j.tetlet.2016.07.086
  • Peer Reviewed
• [Journal Article] Structurally Variable Porous Organic Salt based on Multi-directional Supramolecular Cluster (2016)
  • Author(s): Tetsuya Miyano, Naoki Okada, Ryunosuke Nishida, Atsushi Yamamoto, Ichiro Hisaki, Norimitsu Tohnai
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 43 Pages: 15430-15436
  • DOI: 10.1002/chem.201602233
  • Peer Reviewed
• [Journal Article] Template Synthesis of Decaphyrin without Meso-Bridges: Cyclo[10]pyrrole (2016)
  • Author(s): T. Okujima, C. Ando, S. Agrawal, H. Matsumoto, S. Mori, K. Ohara, I. Hisaki, T. Nakae, M. Takase, H. Uno, and N. Kobayashi
  • Journal Title: journal of the American Chemical Society Volume: 138 Issue: 24 Pages: 7540-7543
  • DOI: 10.1021/jacs.6b04941
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Alignment of Paired Molecules of C60 within a Hexagonal Platform Networked through Hydrogen-Bonds (2016)
  • Author(s): Ichiro Hisaki, Shoichi Nakagawa, Hiroyasu Sato, Norimitsu Tohnai
  • Journal Title: Chem. Commun. Volume: 52 Issue: 63 Pages: 9781-9784
  • DOI: 10.1039/c6cc04310k
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Doubly N-Methylated Porphyrinoids (2016)
  • Author(s): Wakana Naito, Nobuhiro Yasuda, Tatsuki Morimoto, Yasuteru Shigeta, Hikaru Takaya, Ichiro Hisaki, Hiromitsu Maeda
  • Journal Title: Org. Lett. Volume: 18 Issue: 12 Pages: 3006-3009
  • DOI: 10.1021/acs.orglett.6b01377
  • Peer Reviewed
• [Journal Article] Photoinduced electron transfer in porous organic salt crystals impregnated with fullerenes (2016)
  • Author(s): Tetsuya Hasegawa, Kei Ohkubo, Ichiro Hisaki, Mikiji Miyata, Norimitsu Tohnai, Shunichi Fukuzumi
  • Journal Title: Chem. Commun. Volume: 52 Issue: 51 Pages: 7928-7931
  • DOI: 10.1039/c6cc02377k
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] A Series of Layered Assemblies of Hydrogen-Bonded, Hexagonal Networks of C3-Symmetric π-Conjugated Molecules: A Potential Motif of Porous Organic Materials (2016)
  • Author(s): I. Hisaki, S. Nakagawa, N. Ikenaka, Y. Imamura, M. Katouda, M. Tashiro, H. Tsuchida, T. Ogoshi, H. Sato, N. Tohnai, M. Miyata
  • Journal Title: Journal of American Chemical Society Volume: 印刷中 Issue: 20 Pages: 6617-6628
  • DOI: 10.1021/jacs.6b02968
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] NiII Tetrahydronorcorroles: Antiaromatic Porphyrinoids with Saturated Pyrrole Units (2016)
  • Author(s): Ryo Nozawa, Keitaro Yamamoto, Ichiro Hisaki, Ji-Young Shin, Hiroshi Shinokubo
  • Journal Title: Chem. Commun. Volume: 52 Issue: 44 Pages: 7106-7109
  • DOI: 10.1039/c6cc02918c
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] 水素結合でくみ上げた多孔性二次元シートの積層構造 (2016)
  • Author(s): 久木一朗
  • Journal Title: 日本結晶学会誌 Volume: 58 Pages: 209-214
  • NAID: 130005267917
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Arrangement Modulation of pi-Stacked Columnar Assemblies of Octadehydrodibenzo[12]annulene: Substituent Effects of Peripheral Thienyl and Phenyl Rings (2016)
  • Author(s): Ichiro Hisaki, Keisuke Osaka, Nobuaki Ikenaka, Akinori Saeki, Norimitsu Tohnai, Shu Seki, Mikiji Miyata
  • Journal Title: Cryst. Growth Des. Volume: 16 Issue: 2 Pages: 714-721
  • DOI: 10.1021/acs.cgd.5b01273
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Polymorphs of Layered Assemblies of Hydrogen-Bonded Hexagonal Networks Caused by Conformational Frustration (2016)
  • Author(s): Ichiro Hisaki, Nobuaki Ikenaka, Norimitsu Tohnai, Mikiji Miyata
  • Journal Title: Chem. Commun. Volume: 52 Issue: 2 Pages: 300-303
  • DOI: 10.1039/c5cc07690k
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Chirality Generation in Supramolecular Clusters: Analogues of Octacoordinated Polyhedrons (2015)
  • Author(s): Toshiyuki Sasaki, Yoko Ida, Tetsuharu Yuge, Atsushi Yamamoto, Ichiro Hisaki, Norimitsu Tohnai, Mikiji Miyata
  • Journal Title: Crystal Growth & Design Volume: 15 Issue: 2 Pages: 658-665
  • DOI: 10.1021/cg5013445
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Right-handed 2/1 Helical Arrangement of Benzene Molecules in Cholic Acid Crystal Established by Experimental and Theoretical Circular Dichroism Spectroscopy (2015)
  • Author(s): Heng Wang, Adriana Pietropaolo, Sheng Wang, Chen-Yi Chou, Ichiro Hisaki, Normitsu Tohnai, Mikiji Miyata, Tamaki Nakano
  • Journal Title: RSC Adv. Volume: 5 Issue: 122 Pages: 101110-101114
  • DOI: 10.1039/c5ra20853j
  • Peer Reviewed
• [Journal Article] Gelation or Crystallization? Subtle Valance of Structural Factors for Assembly of DBA Derivatives with Methyl Esters (2015)
  • Author(s): Ichiro Hisaki, Eriko Kometani, Norimitsu Tohnai, Mikiji Miyata
  • Journal Title: CrystEngComm Volume: 17 Issue: 42 Pages: 8079-8084
  • DOI: 10.1039/c5ce00778j
  • Peer Reviewed
• [Journal Article] Synthesis of Chiral Assembly from Achiral Octadehydrotribenzo[14]annulene Derivative by Using Twofold Helical Hydrogen Bonding Template (2015)
  • Author(s): Ichiro Hisaki, Eriko Kometani, Hajime Shigemitsu, Norimitsu Tohnai, Mikiji Miyata
  • Journal Title: Synlett Volume: 26 Issue: 11 Pages: 1601-1605
  • DOI: 10.1055/s-0034-1380688
  • Peer Reviewed
• [Presentation] Hexagonally Networked Two-Dimensional Noncovalent Organic Frameworks (2016)
  • Author(s): Ichiro Hisaki, Shoichi Nakagawa, Nobuaki Ikenaka, Norimitsu Tohnai
  • Organizer: Japan-Taiwan Workshop on Nano Science
  • Place of Presentation: Kagoshima, Japan
  • Year and Date: 2016-10-31
  • Int'l Joint Research
• [Presentation] 多孔性ヘキサゴナルネットワーク構造を足場としたフラーレンの配列制御 (2016)
  • Author(s): 久木一朗, 中川祥一, 佐藤寛泰, 藤内謙光
  • Organizer: 第25回有機結晶シンポジウム
  • Place of Presentation: 京都
  • Year and Date: 2016-09-18
• [Presentation] デヒドロアヌレンの結晶工学 (2016)
  • Author(s): 久木一朗
  • Organizer: 第2回有機結晶プレシンポジウム
  • Place of Presentation: 大阪
  • Year and Date: 2016-09-17
  • Invited
• [Presentation] C3対称性π電子系による水素結合性低密度ヘキサゴナルネットの造形 (2016)
  • Author(s): 久木一朗, 中川祥一, 池中伸明, 藤内謙光
  • Organizer: 第27回基礎有機化学討論会
  • Place of Presentation: 広島
  • Year and Date: 2016-09-01
• [Presentation] Construction of Porous Molecular Materials via Designed Hydrogen Bonding Network (2016)
  • Author(s): Ichiro Hisaki
  • Organizer: International Conference on Small Science 2016
  • Place of Presentation: Prague, Czech Republic
  • Year and Date: 2016-06-25
  • Int'l Joint Research / Invited
• [Presentation] Figuration of Layered Assemblies of Porous Hexagonal Networks through Hydrogen Bonds (2016)
  • Author(s): Ichiro Hisaki
  • Organizer: 2nd International Symposium on π-System Figuration
  • Place of Presentation: Saitama, Japan
  • Year and Date: 2016-04-14
  • Int'l Joint Research
• [Presentation] Figuration of Layered Assemblies of Hydrogen-Bonded Hexagonal Networks Composed of C3-Symmetric π-Conjugated Hydrocarbons (2016)
  • Author(s): 1.Ichiro Hisaki, Shoichi Nakagawa, Nobuaki Ikenaka, Norimitsu Tohnai, Mikiji Miyata
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 京田辺
  • Year and Date: 2016-03-24
  • Int'l Joint Research
• [Presentation] Arrangement Modulation of pi-Stacked Columnar Assemblies: Substituent Effects of Peripheral Thienyl and Phenyl Rings (2015)
  • Author(s): Ichiro Hisaki, Keisuke Osaka, Norimitsu Tohnai, Mikiji Miyata
  • Organizer: Japan-Taiwan Workshop on Nano Science
  • Place of Presentation: Osaka, Japan
  • Year and Date: 2015-11-13
  • Int'l Joint Research
• [Presentation] 構造フラストレーションがもたらす２次元シート積層型多孔質構造の多形発現 (2015)
  • Author(s): 久木一朗, 池中伸明, 藤内謙光, 宮田幹二
  • Organizer: 有機結晶シンポジウム
  • Place of Presentation: 広島
  • Year and Date: 2015-11-01
  • Int'l Joint Research
• [Presentation] Hydrogen-Bonded Multiporous Hexagonal Networks Composed of C3-Symmetric pi-Conjugated Macrocycles (2015)
  • Author(s): 3.Ichiro Hisaki, Shoichi Nakagawa, Nobuaki Ikenaka, Norimitsu Tohnai, Mikiji Miyata
  • Organizer: 22nd International Conference on the Chemistry of the Organic Solid State
  • Place of Presentation: Niigata, Japan
  • Year and Date: 2015-07-12
  • Int'l Joint Research
• [Presentation] Triangular Aromatics-Based, Hydrogen-Bonded, Multiporous Hexagonal Networks as Motif of Porous Molecular Crystals (2015)
  • Author(s): Ichiro Hisaki, Shoichi Nakagawa, Nobuaki Ikenaka, Norimitsu Tohnai, Mikiji Miyata
  • Organizer: 16th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Madrid, Spain
  • Year and Date: 2015-07-05
  • Int'l Joint Research
• [Remarks] 研究室ホームページ
  • URL: http://www.mls.eng.osaka-u.ac.jp/~mol_rec/index_J.html