Development of dynamic covalent radicals for molecular self organization

• Project/Area Number: 17H04874
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Functional solid state chemistry
• Research Institution: Osaka Prefecture University (2018-2020); Kyoto University (2017)
• Principal Investigator: Sakamaki Daisuke 大阪府立大学, 理学(系)研究科(研究院), 助教 (60722741)
• Project Period (FY): 2017-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥24,440,000 (Direct Cost: ¥18,800,000、Indirect Cost: ¥5,640,000); Fiscal Year 2019: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2018: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000); Fiscal Year 2017: ¥13,390,000 (Direct Cost: ¥10,300,000、Indirect Cost: ¥3,090,000)
• Keywords: 有機ラジカル / 動的共有結合 / 芳香族アミン / 自己組織化 / サーモクロミズム / σ二量化 / π二量化 / 近赤外吸収 / クロミズム / 二量化

Outline of Final Research Achievements

we demonstrate that the dimerization behavior of amine-substituted dicyanomethyl radicals can be switched from s- to pi-dimerization simply by varying the
electron-donating substituents. The dicyanomethyl radical with the julolidine skeleton does not undergo sigma-dimerization and was isolated as a stable radical in spite of the absence of bulky protecting groups. X-ray single-crystal analysis revealed that this radical forms the pi-dimer in the crystalline state, and variable temperature spectroscopy showed that this radical is in equilibrium
with the p-dimer in toluene solution. DFT calculations point to the importance of electrostatic interactions as a driving force for the pi-dimerization of this radical because of its polarized structure.

Academic Significance and Societal Importance of the Research Achievements

本研究によって、共有結合の断片であるラジカルがどのように二量化するかをコントロールするための分子設計指針を得ることが出来た。本研究で得られた知見は、有機ラジカルを分子の自己組織化や、外部刺激に応答して性質が変化する機能性材料などへと応用するための有効な指針となると考えられる。

Research Products

• [Journal Article] Dicyanomethyl Radical-Based Near-Infrared Thermochromic Dyes with High Transparency in the Visible Region (2019)
  • Author(s): Okino Kohei、Sakamaki Daisuke、Seki Shu
  • Journal Title: ACS Materials Letters Volume: 1 Issue: 1 Pages: 25-29
  • DOI: 10.1021/acsmaterialslett.9b00049
  • Peer Reviewed
• [Journal Article] Extreme Multi-Point van der Waals Interaction: Isolable Dimers of Phthalocyanines Substituted with Pillar-like Azaacenes (2019)
  • Author(s): H. Saeki, D. Sakamaki, H. Fujiwara, S. Seki
  • Journal Title: Chemical Science Volume: 10 Issue: 39 Pages: 8939-8945
  • DOI: 10.1039/c9sc01739a
  • NAID: 120006895585
  • Peer Reviewed / Open Access
• [Journal Article] Dynamic covalent bonds: approaches from stable radical species (2019)
  • Author(s): Sakamaki Daisuke、Ghosh Samrat、Seki Shu
  • Journal Title: Materials Chemistry Frontiers Volume: 3 Issue: 11 Pages: 2270-2282
  • DOI: 10.1039/c9qm00488b
  • Peer Reviewed
• [Journal Article] Electronic and Photophysical Properties of 9,10-Anthrylene-Bridged B-π-N Donor-Acceptor Molecules with Solid-State Emission in the Yellow to Red Region (2019)
  • Author(s): Uebe Masashi、Sakamaki Daisuke、Ito Akihiro
  • Journal Title: ChemPlusChem Volume: 印刷中 Issue: 9 Pages: 1305-1313
  • DOI: 10.1002/cplu.201900003
  • Peer Reviewed
• [Journal Article] Formation of Cyclophane Macrocycles in Carbazole-Based Biradicaloids: Impact of the Dicyanomethylene Substitution Position (2019)
  • Author(s): I. Badテュa-Domテュnguez, A. Perez-Guardiola, J. C. Sancho-Garcテュa, J. T. L. Navarrete, V. H. Jolテュn, H. Li, D. Sakamaki, S. Seki, and M. C. R. Delgado
  • Journal Title: ACS Omega Volume: 4(3) Issue: 3 Pages: 4761-4769
  • DOI: 10.1021/acsomega.8b03418
  • Peer Reviewed / Open Access
• [Journal Article] Hash-Mark-Shaped Azaacene Tetramers with Axial Chirality (2018)
  • Author(s): Y. Inoue, D. Sakamaki, Y. Tsutsui, M. Gon, Y. Chujo, and S. Seki
  • Journal Title: J. Am. Chem. Soc. Volume: 140(23) Issue: 23 Pages: 7152-7158
  • DOI: 10.1021/jacs.8b02689
  • Peer Reviewed
• [Journal Article] Comparison of Radical Generation Efficiencies of the Oxime-Based Initiator Radicals Using Galvinoxyl Radical as an Indicator (2018)
  • Author(s): A. Tsuneishi, D. Sakamaki, Q. Gao, T. Shoda, T. Kozawa, and S. Seki
  • Journal Title: Jpn. J. Appl. Phys Volume: 57(8) Issue: 8 Pages: 86504-86504
  • DOI: 10.7567/jjap.57.086504
  • NAID: 210000149427
  • Peer Reviewed
• [Journal Article] Landscape of Charge Carrier Transport in Doped Poly(3-hexylthiophene): Noncontact Approach Using Ternary Combined Dielectric, Paramagnetic, and Optical Spectroscopies (2018)
  • Author(s): Tsutsui Yusuke、Okamoto Haruka、Sakamaki Daisuke、Sugiyasu Kazunori、Takeuchi Masayuki、Seki Shu
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 9 Issue: 13 Pages: 3639-3645
  • DOI: 10.1021/acs.jpclett.8b01465
  • Peer Reviewed
• [Journal Article] Highly Fluorescent Liquid Crystals from Excited-State Intramolecular Proton Transfer Molecules (2018)
  • Author(s): Zhang Wanying、Sakurai Tsuneaki、Aotani Mika、Watanabe Go、Yoshida Hiroyuki、Padalkar Vikas S.、Tsutsui Yusuke、Sakamaki Daisuke、Ozaki Masanori、Seki Shu
  • Journal Title: Advanced Optical Materials Volume: 7 Issue: 2 Pages: 1801349-1801349
  • DOI: 10.1002/adom.201801349
  • Peer Reviewed
• [Journal Article] High Pressure Synthesis of Hydride-fluoride Pyrochlore NaCaMg2F7?xHx (2018)
  • Author(s): Arai Kazunari、Kobayashi Yoji、Tang Ya、Tsutsui Yusuke、Sakamaki Daisuke、Yamamoto Takafumi、Fujii Kotaro、Yashima Masatomo、Seki Shu、Kageyama Hiroshi
  • Journal Title: Chemistry Letters Volume: 47 Issue: 7 Pages: 829-832
  • DOI: 10.1246/cl.180256
  • NAID: 130007402828
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Unique Cohesive Nature of β1-isomer of [70]PCBM Fullerene on Structures and Photovoltaic Performances of Bulk Heterojunction Films with PffBT4T-2OD Polymer (2018)
  • Author(s): T. Umeyama, K. Igarashi, D. Sakamaki, S. Seki, and H. Imahori
  • Journal Title: Chem. Commun. Volume: 54 Issue: 4 Pages: 405-408
  • DOI: 10.1039/c7cc08947c
  • Peer Reviewed
• [Journal Article] Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C60 (2018)
  • Author(s): H. Yokoi, S. Hiroto, D. Sakamaki, S. Seki, H. Shinokubo
  • Journal Title: Chem. Sci. Volume: 9 Issue: 4 Pages: 819-824
  • DOI: 10.1039/c7sc04453d
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and properties of a twin donor molecule composed of cofacially stacked dihydrodiazapentacenes (2018)
  • Author(s): D. Sakamaki, H. Saeki, S. Seki
  • Journal Title: Materials Chemistry Frontiers Volume: 2 Issue: 3 Pages: 530-536
  • DOI: 10.1039/c7qm00563f
  • Peer Reviewed
• [Journal Article] Tuning of Open-shell Characters of a Terphenoquinone by Introducing a Benzodithiophene Unit (2017)
  • Author(s): H. Tomita, D. Sakamaki, M. Noguchi, M. Nakano, S. Seki
  • Journal Title: Chemistry Lettrs Volume: 46 Issue: 6 Pages: 805-807
  • DOI: 10.1246/cl.170128
  • NAID: 130005689372
  • Peer Reviewed
• [Journal Article] Modulation of Open-Shell Characters of Amine-inserted Diphenoquinones via Structural Modification (2017)
  • Author(s): Y. Matsuta, D. Sakamaki, R. Kurata, A. Ito, S. Seki
  • Journal Title: Chemistry An Asian Journal Volume: 12 Issue: 15 Pages: 1889-1894
  • DOI: 10.1002/asia.201700652
  • Peer Reviewed
• [Journal Article] Optical and Structural Properties of ESIPT Inspired HBT-Fluorene Molecular Aggregates and Liquid Crystals (2017)
  • Author(s): V. S. Padalkar, Y. Tsutsui, T. Sakurai, D. Sakamaki, N. Tohnai, K. Kato, M. Takata, T. Akutagawa, K.-i. Sakai, S. Seki
  • Journal Title: J. Phys. Chem. B Volume: 121 Issue: 45 Pages: 10407-10416
  • DOI: 10.1021/acs.jpcb.7b08073
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] The Divergent Dimerization Behavior of N-Substituted Dicyanomethyl Radicals: Dynamically Stabilized versus Stable Radicals (2017)
  • Author(s): K. Okino, S. Hira, Y. Inoue, D. Sakamaki, S. Seki
  • Journal Title: Angewandte Chemie International Edition Volume: 56 Issue: 52 Pages: 16597-16601
  • DOI: 10.1002/anie.201710354
  • Peer Reviewed
• [Journal Article] Tetraaza[14]- and Octaaza[18]paracyclophane: Synthesis and Characterization of Their Neutral and Cationic States (2017)
  • Author(s): D. Sakamaki, A. Ito, Y. Tsutsui, S. Seki
  • Journal Title: Journal of Organic Chemistry Volume: 82 Issue: 24 Pages: 13348-13358
  • DOI: 10.1021/acs.joc.7b02437
  • Peer Reviewed
• [Presentation] 非局在化したラジカルを有するTTFの合成・構造・電子物性 (2019)
  • Author(s): 三岡味紗稀、酒巻大輔、藤原秀紀
  • Organizer: 第３０回基礎有機化学討論会
• [Presentation] 異なる位置で連結したジアザテトラセン二量体の合成と電子的性質 (2019)
  • Author(s): 田中克輝、酒巻大輔、藤原秀紀
  • Organizer: 第３０回基礎有機化学討論会
• [Presentation] 含窒素複素環を置換したTTF誘導体を用いた複合機能性物質の開発 (2019)
  • Author(s): 西村友樹、酒巻大輔、藤原秀紀
  • Organizer: 第１３回分子科学討論会
• [Presentation] 含窒素複素環を置換したTTF誘導体を用いた複合機能性物質の開発 (2019)
  • Author(s): 西村友樹・山口美奈代・酒巻大輔・藤原秀紀
  • Organizer: 日本化学会第99春季年会
• [Presentation] ジアザフルオレノンを有するD-A型複合分子を用いた光機能性物質の開発 (2019)
  • Author(s): 松本悠希・酒巻大輔・藤原秀紀
  • Organizer: 日本化学会第99春季年会
• [Presentation] 非局在化したラジカルを有するTTFの合成・構造・電子物性 (2019)
  • Author(s): 三岡美紗稀・酒巻大輔・藤原秀紀
  • Organizer: 日本化学会第99春季年会
• [Presentation] 平面上に固定されたアミノ基を有するジシアノメチルラジカルの電子的性質と近赤外サーモクロミズム (2018)
  • Author(s): 沖野浩平・酒巻大輔・関修平
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] 多重π-π相互作用によるフタロシアニンの選択的二量化と中心金属間磁性相 (2018)
  • Author(s): 佐伯英紀・酒巻大輔・関修平
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] マイクロ波複合分光法を用いたポリチオフェン中の電荷輸送特性評価 (2017)
  • Author(s): 筒井 祐介, 岡本 悠, 崔 旭鎮, 櫻井 庸明, 酒巻 大輔, 関 修平
  • Organizer: 第78回応用物理学会秋季学術講演会
• [Presentation] 電子スピン/誘電損失同時測定による有機半導体キャリアダイナミクス解析 (2017)
  • Author(s): 岡本悠, 筒井祐介, 崔 旭鎮, 酒巻大輔, 櫻井庸明, 関修平
  • Organizer: 第78回応用物理学会秋季学術講演会
• [Presentation] アミノ基を挿入したジフェノキノンの構造と開殻性変調 (2017)
  • Author(s): 酒巻大輔, 松田悠弥, 倉田亮平, 伊藤彰浩, 関 修平
  • Organizer: 第28回基礎有機化学討論会
• [Presentation] アミノ基と共役したジシアノメチルラジカルの電子構造と動的共有結合性 (2017)
  • Author(s): 沖野浩平, 酒巻大輔, 関 修平
  • Organizer: 第28回基礎有機化学討論会
• [Presentation] 周辺部にアザアセン構造を有するフタロシアニンの合成と選択的二量化挙動 (2017)
  • Author(s): 佐伯英紀, 酒巻大輔, 関 修平
  • Organizer: 第28回基礎有機化学討論会
• [Presentation] 平面上に固定されたアミノ基を有するジシアノメチルラジカルの動的二量化 (2017)
  • Author(s): 沖野浩平, 酒巻大輔, 関 修平
  • Organizer: 第4回π造形科学若手研究会
• [Presentation] 多重π-π相互作用を利用したフタロシアニンの選択的二量化 (2017)
  • Author(s): 佐伯英紀, 酒巻大輔, 関 修平
  • Organizer: 第4回π造形科学若手研究会
• [Presentation] Structures and Open-shell Characters of Amine-inserted Diphenoquinones (2017)
  • Author(s): Yuya Matsuta, Daisuke Sakamaki, Ryohei. Kurata, Akihiro Ito, Shu Seki
  • Organizer: 17th International Symposium on Novel Aromatic Compounds
• [Presentation] A #-shaped Azaacene Tetramer with Axial Chirality:Synthesis, Structure and Electronic Properties (2017)
  • Author(s): Yuki Inoue, Daisuke Sakamaki, Shu Seki
  • Organizer: 17th International Symposium on Novel Aromatic Compounds
• [Remarks] わずかな構造の違いで分子のまとまり方が変化 －高大接続プログラムによるユニークな成果－
  • URL: http://www.kyoto-u.ac.jp/ja/research/research_results/2017/171110_3.html
• [Remarks] π造形科学ニュースレター Vol. 42
  • URL: http://pi-figuration.jp/nl/nl_42.pdf