Studeis on Properties of Open-shell Molecular Assembly with Unique Intermolecular Interaction

• Project/Area Number: 17K05783
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Osaka University
• Principal Investigator: Shuichi Suzuki 大阪大学, 基礎工学研究科, 准教授 (80433291)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: ラジカルイオン / 集合構造 / 色調変化 / スピン状態変化 / 相転移 / ラジカルカチオン / ラジカルアニオン / フラストレーション / 流動性

Outline of Final Research Achievements

The purpose of the project is to develop new functional materials using charged open-shell p-electronic molecules. We have succeeded in finding radical cationic species with unique phase transition behaviors. For instance, N-pentylphenothiazine radical cation showed a phase transition accompanying with color and magnetic properties changes (see, ACS Omega 2019, 4, 10031).

Academic Significance and Societal Importance of the Research Achievements

本研究における同電荷ラジカルイオン種集積体における相互作用に関する知見は、これまで見過ごされてきた点である。今回、その部分を積極的に利用することでこれまでに類を見ない新しいタイプの相転移機構を見出すことに成功した。また、高い安定性をもつイオン性ラジカルの液体状態の設計方針も見出すことができた。以上のことから、今後の研究でさらに新しい機能性創出が期待される。

Research Products

• [Int'l Joint Research] Russian Academy of Sciences/Novosibirsk State University(ロシア連邦)
• [Journal Article] Synthesis, Structures, and Properties of Neutral and Radical Cationic S,C,C-Bridged Triphenylamine (2020)
  • Author(s): Shin-ichiro Kato, Takanori Matsuoka, Shuichi Suzuki, Motoko S. Asano, Toshitada Yoshihara, Seiji Tobita, Taisuke Matsumoto, Chitoshi Kitamura
  • Journal Title: Org. Lett. Volume: 22 Issue: 2 Pages: 734-738
  • DOI: 10.1021/acs.orglett.9b04575
  • Peer Reviewed
• [Journal Article] Environmentally Benign Strategy for Arylation of Nitronyl Nitroxide Using a Non-Transition Metal Nucleophile (2020)
  • Author(s): Suzuki Shuichi、Nakamura Fumiya、Naota Takeshi
  • Journal Title: Organic Letters Volume: 22 Issue: 4 Pages: 1350-1354
  • DOI: 10.1021/acs.orglett.9b04655
  • Peer Reviewed
• [Journal Article] Redox‐Induced Modulation of Exchange Interaction in a High‐Spin Ground‐State Diradical/Triradical System (2020)
  • Author(s): Nagata Atsuki、Hiraoka Shinsuke、Suzuki Shuichi、Kozaki Masatoshi、Shiomi Daisuke、Sato Kazunobu、Takui Takeji、Tanaka Rika、Okada Keiji
  • Journal Title: Chemistry -A European Journal Volume: 26 Issue: 14 Pages: 3166-3172
  • DOI: 10.1002/chem.201905465
  • Peer Reviewed
• [Journal Article] Strategy for Stimuli-Induced Spin Control Using a Liquescent Radical Cation (2019)
  • Author(s): Suzuki Shuichi、Maya Ryochi、Uchida Yoshiaki、Naota Takeshi
  • Journal Title: ACS Omega Volume: 4 Issue: 6 Pages: 10031-10035
  • DOI: 10.1021/acsomega.9b00982
  • Peer Reviewed / Open Access
• [Journal Article] Structures and Electronic Properties of Diisopropylaminoborane Substituted with Highly Electron-Rich π-Conjugated Systems and Their Oxidized States (2019)
  • Author(s): Yoshida Kohei、Suzuki Shuichi、Kozaki Masatoshi、Okada Keiji
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 92 Issue: 11 Pages: 1902-1909
  • DOI: 10.1246/bcsj.20190199
  • NAID: 130007745889
  • Peer Reviewed
• [Journal Article] Triplet Diradical Cation Salts Consisting of Phenothiazine Radical Cation and Nitronyl Nitroxide (2019)
  • Author(s): Tahara Takuma、Suzuki Shuichi、Kozaki Masatoshi、Shiomi Daisuke、Sugisaki Kenji、Sato Kazunobu、Takui Takeji、Mitake Yota、Hosokoshi Yuko、Nojiri Hiroyuki、Okada Keiji
  • Journal Title: Chemistry - A European Journal Volume: 印刷中 Issue: 29 Pages: 7201-7209
  • DOI: 10.1002/chem.201900513
  • Peer Reviewed
• [Journal Article] Radical Metalloids with N-Heterocyclic Carbene and Phenanthroline Ligands: Synthesis, Properties, and Cross-Coupling Reaction of [(Nitronyl Nitroxide)-2-ido]metal Complexes with Aryl Halides (2018)
  • Author(s): Yamada Kiyomi、Zhang Xun、Tanimoto Ryu、Suzuki Shuichi、Kozaki Masatoshi、Tanaka Rika、Okada Keiji
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 印刷中 Issue: 7 Pages: 1150-1157
  • DOI: 10.1246/bcsj.20180033
  • NAID: 130007404812
  • Peer Reviewed
• [Journal Article] Chemical Stability of the 5-Mesityl-5′′-(nitronyl nitroxide)-2,2′:5′,2′′-ter(3,4-ethylenedioxythiophene) Radical Cation (2018)
  • Author(s): Tahara Takuma、Suzuki Shuichi、Kozaki Masatoshi、Nishinaga Tohru、Okada Keiji
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 91 Issue: 8 Pages: 1193-1195
  • DOI: 10.1246/bcsj.20180078
  • NAID: 130007433399
  • Peer Reviewed
• [Journal Article] Radical Cation π-Dimers of Conjugated Oligomers as Molecular Wires: An Analysis Based on Nitronyl Nitroxide Spin Labels (2018)
  • Author(s): Nishinaga Tohru、Kanzaki Yuki、Shiomi Daisuke、Matsuda Kenji、Suzuki Shuichi、Okada Keiji
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 45 Pages: 11717-11728
  • DOI: 10.1002/chem.201801712
  • NAID: 120006716400
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019731
  • Peer Reviewed
• [Journal Article] Preparation and Properties of a Polycyclic p-Quinodimethane with Two Oxygen Bridges and its Radical Cation in Comparison with the Isomeric o-Quinodimethane (2018)
  • Author(s): Sato Chihiro、Suzuki Shuichi、Okada Keiji、Kozaki Masatoshi
  • Journal Title: Chemistry - An Asian Journal Volume: 13 Issue: 23 Pages: 3729-3736
  • DOI: 10.1002/asia.201801269
  • NAID: 120006826375
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019735
  • Peer Reviewed
• [Journal Article] Synthesis and Magnetic Properties of (Pyrrolidin-1-oxyl)-(Nitronyl Nitroxide)/(Iminonitroxide)-Dyads (2018)
  • Author(s): Tsujimoto Haruki、Suzuki Shuichi、Kozaki Masatoshi、Shiomi Daisuke、Sato Kazunobu、Takui Takeji、Okada Keiji
  • Journal Title: Chemistry - An Asian Journal Volume: 印刷中 Issue: 10 Pages: 1801-1806
  • DOI: 10.1002/asia.201801615
  • Peer Reviewed
• [Journal Article] Group 11 Metal Complexes Coordinated by the (Nitronyl Nitroxide)-2-ide Radical Anion: Facile Oxidation of Stable Radicals Controlled by Metal-Carbon Bonds in Radical-Metalloids (2018)
  • Author(s): Tanimoto Ryu、Yamada Kiyomi、Suzuki Shuichi、Kozaki Masatoshi、Okada Keiji
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2018 Issue: 10 Pages: 1198-1203
  • DOI: 10.1002/ejic.201800038
  • Peer Reviewed
• [Journal Article] A direct synthetic method for (nitronyl nitroxide)-substituted π-electronic compounds via a palladium-catalyzed cross-coupling reaction with a zinc complex (2018)
  • Author(s): Suzuki Shuichi、Nakamura Fumiya、Naota Takeshi
  • Journal Title: Materials Chemistry Frontiers Volume: 2 Issue: 3 Pages: 591-596
  • DOI: 10.1039/c7qm00565b
  • Peer Reviewed
• [Journal Article] Synthesis and Magnetic Properties of Trioxytriphenylamine Dimers in their Di(radical cationic) States (2017)
  • Author(s): Suzuki Shuichi、Tanaka Nobuaki、Kozaki Masatoshi、Shiomi Daisuke、Sato Kazunobu、Takui Takeji、Okada Keiji
  • Journal Title: Chemistry - A European Journal Volume: 23 Issue: 63 Pages: 16014-16025
  • DOI: 10.1002/chem.201703220
  • Peer Reviewed
• [Journal Article] Oxidation State-Dependent Intramolecular Electronic Interaction of Carbazole-Based Azacyclophanes with 9,10-Anthrylene Units (2017)
  • Author(s): Iwanaga Tetsuo、Yamauchi Tomokazu、Toyota Shinji、Suzuki Shuichi、Okada Keiji
  • Journal Title: The Journal of Organic Chemistry Volume: 82 Issue: 19 Pages: 10699-10703
  • DOI: 10.1021/acs.joc.7b01688
  • Peer Reviewed
• [Journal Article] (Azulene-1,3-diyl)-bis(nitronyl nitroxide) and (Azulene-1,3-diyl)-bis(iminonitroxide) and Their Copper Complexes (2017)
  • Author(s): Haraguchi Makoto、Tretyakov Evgeny、Gritsan Nina、Romanenko Galina、Gorbunov Dmitry、Bogomyakov Artem、Maryunina Kseniya、Suzuki Shuichi、Kozaki Masatoshi、Shiomi Daisuke、Sato Kazunobu、Takui Takeji、Nishihara Sadafumi、Inoue Katsuya、Okada Keiji
  • Journal Title: Chemistry - An Asian Journal Volume: 12 Issue: 22 Pages: 2929-2941
  • DOI: 10.1002/asia.201701085
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Stereoelectronic control of oxidation potentials of 3,7-bis(diarylamino)phenothiazines (2017)
  • Author(s): Karimata Ayumu、Suzuki Shuichi、Kozaki Masatoshi、Okada Keiji
  • Journal Title: RSC Advances Volume: 7 Issue: 88 Pages: 56144-56152
  • DOI: 10.1039/c7ra12600j
  • Peer Reviewed / Open Access
• [Journal Article] π-System Figuration for Open-shell Molecules Based on Nitronyl Nitroxide (2017)
  • Author(s): 鈴木 修一、小嵜 正敏、岡田 惠次
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 75 Issue: 9 Pages: 955-964
  • DOI: 10.5059/yukigoseikyokaishi.75.955
  • NAID: 130006068826
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed
• [Presentation] マルチラジカル分子システム：スピン状態制御と機能開拓 (2020)
  • Author(s): 鈴木修一
  • Organizer: 令和元年度第5回岡山理科大学プロジェクト研究推進事業講演会
  • Invited
• [Presentation] テトラチアフルバレンラジカルカチオン塩の構造および刺激応答光学特性 (2020)
  • Author(s): 阪井俊裕・鈴木修一・内田幸明・直田 健
  • Organizer: 第100日本化学会春季年会
• [Presentation] ビス(ニトロニルニトロキシド)金(I)錯体の電気化学的および磁気的性質 (2020)
  • Author(s): 大野智也・和田知之・鈴木 修一・小嵜正敏・岡田惠次・佐藤和信・塩見大輔・工位武治・直田 健
  • Organizer: 第100日本化学会春季年会
• [Presentation] アルキル鎖末端をフェノチアジンで修飾したジラジカルカチオンの刺激応答磁気特性 (2020)
  • Author(s): 内田瑞貴・鈴木修一・直田 健
  • Organizer: 第100日本化学会春季年会
• [Presentation] Changes in Physical Properties of Phenothiazine Radical Cations During Solid-liquid-solid Phase Transitions (2019)
  • Author(s): Shuichi Suzuki, Ryochi Maya, Yoshiaki Uchida, Takeshi Naota
  • Organizer: The 13th Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
  • Int'l Joint Research / Invited
• [Presentation] Unique Phase Transition of N-Pentylphenothiazine Radical Cation (2019)
  • Author(s): Shuichi Suzuki, Ryochi Maya, Yoshiaki Uchida, Takeshi Naota
  • Organizer: The 6th Awaji International Workshop on “Electron Spin Science & Technology: Biological and Materials Science Oriented Applications”
  • Int'l Joint Research / Invited
• [Presentation] スピン状態制御を目指した分子システムの創製 (2019)
  • Author(s): 鈴木修一
  • Organizer: 令和元年 基礎工学部談話会：分子と情報：量子で広がる最新の研究
  • Invited
• [Presentation] 液状化可能なフェノチアジンラジカルカチオン誘導体の物性 (2019)
  • Author(s): 真屋良地・鈴木修一・内田幸明・直田 健
  • Organizer: 第46回有機典型元素化学討論会
• [Presentation] 刺激応答性フェノチアジンラジカルカチオン塩の創製 (2019)
  • Author(s): 真屋良地・鈴木修一・内田幸明・直田 健
  • Organizer: 先端研究基盤共用促進事業 大阪大学ナノ構造量子解析ソリューション成果報告会
• [Presentation] 刺激応答性をもつテトラチアフルバレンラジカルカチオンの創成 (2019)
  • Author(s): 阪井俊裕・鈴木修一・内田幸明・直田 健
  • Organizer: 第30回基礎有機化学討論会
• [Presentation] ビス(ニトロニルニトロキシド)金(I)錯体の合成と構造 (2019)
  • Author(s): 大野智也・和田知之・鈴木 修一・小嵜正敏・岡田惠次・佐藤和信・塩見大輔・工位武治・直田 健
  • Organizer: 第30回基礎有機化学討論会
• [Presentation] 液状化可能なジヒドロフェナジンラジカルカチオン塩の相転移挙動 (2019)
  • Author(s): 山口大樹・鈴木修一・内田幸明・直田 健
  • Organizer: 第30回基礎有機化学討論会
• [Presentation] A Liquescent Radical Cation and Its Unique Phase Transition Behavior (2019)
  • Author(s): Shuichi Suzuki, Ryochi Maya, Yoshiaki Uchida, Takeshi Naota
  • Organizer: 18th International Conference on Novel Aromatic Compounds
  • Int'l Joint Research
• [Presentation] パラジウム触媒を用いた無置換ニトロニルニトロキシドの直接アリール化 (2019)
  • Author(s): 中村文哉・鈴木修一・直田 健
  • Organizer: 日本化学会第99春季年会
• [Presentation] 特異な刺激応答性を示すテルピリジン白金(II)型カチオン性錯体の光物性 (2019)
  • Author(s): 澤木友利華・鈴木修一・直田 健
  • Organizer: 日本化学会第99春季年会
• [Presentation] 固液相転移を示すトランス-ビス(サリチルアルジミナト)白金錯体の発光特性 (2019)
  • Author(s): 杉浦 奨・鈴木修一・直田 健
  • Organizer: 日本化学会第99春季年会
• [Presentation] 固液相転移を伴うN-アルキルフェノチアジンラジカルカチオンの物性変化 (2019)
  • Author(s): 真屋良地・鈴木修一・内田幸明・直田 健
  • Organizer: 日本化学会第99春季年会
• [Presentation] 固液相転移を示すジヒドロフェナジンラジカルカチオンの光学および磁気的性質 (2019)
  • Author(s): 山口大樹・鈴木修一・内田幸明・直田 健
  • Organizer: 日本化学会第99春季年会
• [Presentation] Unique Phase Transition Behaviors Using a Liquescent N-Pentylphenothiazine Radical Cation Salt (2019)
  • Author(s): Shuichi Suzuki, Ryochi Maya, Yoshiaki Uchida, Takeshi Naota
  • Organizer: 7th International Symposium on π-System Figuration
• [Presentation] 固液相転移を示すイオン性開殻種の独特な色調変化 (2018)
  • Author(s): 鈴木修一
  • Organizer: 第 39 回光化学若手の会
  • Invited
• [Presentation] 固液相転移を利用するイオン種集積体の機能開拓 (2018)
  • Author(s): 鈴木修一
  • Organizer: 2018 構造有機化学研究会
  • Invited
• [Presentation] Recent Progress of Nitronyl Nitroxide and Related Open-shell Molecules (2018)
  • Author(s): Suzuki Shuichi
  • Organizer: Symposium on “Diverse Facets of Chemistry II”
  • Invited
• [Presentation] Properties and Reactivities of (Nitronyl Nitroxide)-Substituted Metal Complexes (2018)
  • Author(s): Suzuki Shuichi
  • Organizer: 2nd Joint Symposium on Materials Research - Diverse Aspects of Future Chemistry -
  • Invited
• [Presentation] Properties of Phenothiazine Radical Cation Salt with Unique Phase Transition Behavior (2018)
  • Author(s): Shuichi Suzuki, Ryochi Maya, Yoshiaki Uchida, Takeshi Naota
  • Organizer: pi-System Figuration European-Japanese Workshop 2018
• [Presentation] 直鎖アルキル置換フェノチアジンラジカルカチオン塩の相転移を伴う色調変化 (2018)
  • Author(s): 真屋良地・鈴木修一・内田幸明・直田 健
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] 無置換ニトロニルニトロキシドの触媒的アリール化 (2018)
  • Author(s): 中村文哉・鈴木修一・直田 健
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] 結晶-液体転移を示すジヒドロフェナジンラジカルカチオン塩 (2018)
  • Author(s): 山口大樹・鈴木修一・内田幸明・直田 健
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] パラジウム触媒を用いた無置換ニトロニルニトロキシドの直接官能基化 (2018)
  • Author(s): 中村文哉、鈴木修一、直田 健
  • Organizer: 日本化学会第98春季年会
• [Presentation] フェノチアジンラジカルカチオン塩の構造相転移に基づく特異な色調変化 (2018)
  • Author(s): 真屋良地、鈴木修一、内田幸明、直田 健
  • Organizer: 日本化学会第98春季年会
• [Presentation] 可溶性ビス(トリオキシトリフェニルアミン)誘導体の合成と性質 (2018)
  • Author(s): 下出健人、鈴木修一、小嵜正敏、岡田惠次
  • Organizer: 日本化学会第98春季年会
• [Presentation] Synthesis and Properties of Trioxytriphenylamine Dimers (2017)
  • Author(s): Suzuki Shuichi、Tanaka Nobuaki、Kozaki Masatoshi、Shiomi Daisuke、Sato Kazunobu、Takui Takeji、Okada Keiji
  • Organizer: p-System Figuration German-Japanese Workshop Heidelberg
  • Int'l Joint Research / Invited
• [Presentation] ニトロニルニトロキシドを基盤とした開殻性有機金属種の合成と性質 (2017)
  • Author(s): 鈴木修一
  • Organizer: 第５回有機化学若手シンポジウム
  • Invited
• [Presentation] スピン制御型光電荷分離を目指した分子システムの設計と合成 (2017)
  • Author(s): 鈴木修一
  • Organizer: 2017年電気化学秋季大会
  • Invited
• [Presentation] 開殻π造形：新奇合成法とスピン制御法 (2017)
  • Author(s): 鈴木修一
  • Organizer: 京都大学大学院分子工学専攻 第 276 回分子工学コロキウム
  • Invited
• [Presentation] 新奇機能性を指向したラジカルカチオン塩の設計新奇機能性を指向したラジカルカチオン塩の設計 (2017)
  • Author(s): 鈴木修一
  • Organizer: 構造有機化学若手研究者研究会2017
• [Presentation] N-ペンチルフェノチアジンラジカルカチオン塩の特異な相転移挙動 (2017)
  • Author(s): 真屋良地、鈴木修一、内田幸明、直田 健
  • Organizer: 第28回基礎有機化学討論会
• [Presentation] 亜鉛試薬を用いた芳香族ニトロニルニトロキシドの直接合成法 (2017)
  • Author(s): 中村文哉、鈴木修一、直田 健
  • Organizer: 第28回基礎有機化学討論会
• [Remarks] 液状化可能なラジカルカチオン種を利用した刺激によるスピン情報変換戦略
  • URL: http://suzukishuichi.material.jp/ocu_poc/?page_id=249