Development of helical phthalocyanine analogues

• Project/Area Number: 20H02728
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Muranaka Atsuya 国立研究開発法人理化学研究所, 環境資源科学研究センター, 専任研究員 (20374902)
• Project Period (FY): 2020-04-01 – 2024-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥18,070,000 (Direct Cost: ¥13,900,000、Indirect Cost: ¥4,170,000); Fiscal Year 2023: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2022: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2021: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2020: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000)
• Keywords: フタロシアニン / らせん / 円偏光発光 / キラリティー

Outline of Research at the Start

フタロシアニンは平面環状の２次元π共役構造をもつ化合物であり、様々な機能性を有するため基礎・応用の両面から精力的に研究されている。本研究では、通常のフタロシアニン系化合物には見られない３次元らせん構造をもつフタロシアニン系化合物の合成化学・配位化学を追求し、未知の機能性を開拓することを目的とする。学理の追求を目指した１）新規誘導体の合成、２）多彩な金属錯体の合成、機能性開拓を目指した３）円偏光発光（CPL） 特性の向上、４）半導体特性の評価、５）不斉触媒の評価、を中心に研究を展開する。

Outline of Final Research Achievements

Phthalocyanines are an important class of two-dimensional planar cyclic π-conjugated molecules and have attracted much interest from fundamental and practical aspects. This project focused on synthesis and properties of novel phthalocyanine analogues with three-dimensional nonplanar noncyclic structures. It was found that most of the synthesized phthalocyanine analogues adopt a flexible helical structure. Circularly polarized luminescence active molecules and chirality-sensing molecules have been developed by utilizing the unique molecular and electronic structures.

Academic Significance and Societal Importance of the Research Achievements

らせん構造をもつπ電子系分子はそのユニークな構造から基礎学術的に興味がもたれるだけでなく、円偏光発光性分子や不斉触媒分子など機能性分子としての応用にも興味がもたれている。本研究では従来研究対象として注目されていなかったフタロシアニン系らせん化合物に対して実験と理論の両面から研究を展開し、分子構造と物性との相関関係に関する知見を深め、高付加価値π電子系らせん分子の設計指針を提供することができた。

Research Products

• [Journal Article] 20π‐Electron Antiaromatic Benziphthalocyanines with Absorption Reaching the Near‐Infrared‐II Region (2024)
  • Author(s): Yanagi Shunsuke、Takayama Orie、Toriumi Naoyuki、Muranaka Atsuya、Hashizume Daisuke、Uchiyama Masanobu
  • Journal Title: Chemistry -A European Journal Volume: 30 Issue: 29
  • DOI: 10.1002/chem.202400401
  • Peer Reviewed
• [Journal Article] A Switchable Near‐Infrared‐Absorbing Dye Based on Redox‐Bistable Benzitetraazaporphyrin (2023)
  • Author(s): Yanagi Shunsuke、Matsumoto Akihisa、Toriumi Naoyuki、Tanaka Yusuke、Miyamoto Kazunori、Muranaka Atsuya、Uchiyama Masanobu
  • Journal Title: Angewandte Chemie International Edition Volume: 62 Issue: 11
  • DOI: 10.1002/anie.202218358
  • Peer Reviewed
• [Journal Article] Synthesis of isoindole-diimine and its derivatives without ammonia gas bubbling (2023)
  • Author(s): Igarashi Yumiko、Okada Yusuke、Muranaka Atsuya、Suzuki Masahiro、Kobayashi Nagao
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 27 Issue: 01n04 Pages: 423-433
  • DOI: 10.1142/s1088424623500116
  • Peer Reviewed
• [Journal Article] Formation of a dinuclear zinc complex with open-ring hemiporphyrazine (2023)
  • Author(s): Yusuke Tanaka, Xingmei Ouyang, Tomotaka Murayama, Atsuya Muranaka, and Masanobu Uchiyama
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 27 Issue: 01n04 Pages: 184-189
  • DOI: 10.1142/s1088424622500791
  • Peer Reviewed
• [Journal Article] Anti-Kasha emissions of single molecules in a plasmonic nanocavity (2022)
  • Author(s): Imada Hiroshi、Imai-Imada Miyabi、Ouyang Xingmei、Muranaka Atsuya、Kim Yousoo
  • Journal Title: The Journal of Chemical Physics Volume: 157 Issue: 10 Pages: 104302-104302
  • DOI: 10.1063/5.0102087
  • Peer Reviewed
• [Journal Article] Naked-Eye-Detectable Supramolecular Sensing System for Glutaric Acid and Isophthalic Acid (2022)
  • Author(s): Muranaka Atsuya、Ban Hayato、Naito Masaya、Miyagawa Shinobu、Ueda Masahiro、Yamamoto Shin、Harada Mei、Takaya Hikaru、Kimura Masaki、Kobayashi Nagao、Uchiyama Masanobu、Tokunaga Yuji
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 95 Issue: 10 Pages: 1428-1437
  • DOI: 10.1246/bcsj.20220195
  • Peer Reviewed
• [Journal Article] Studies for Absolute Configuration of Chiral 2,6-Cuneanedicarboxylic Acid Esters (2022)
  • Author(s): Hiyori Takebe, Atsuya Muranaka, Masanobu Uchiyama, Seijiro Matsubara
  • Journal Title: Chemistry Letters Volume: 51 Issue: 7 Pages: 754-755
  • DOI: 10.1246/cl.220197
  • Peer Reviewed
• [Journal Article] Orbital-resolved visualization of single-molecule photocurrent channels (2022)
  • Author(s): Imai-Imada Miyabi、Imada Hiroshi、Miwa Kuniyuki、Tanaka Yusuke、Kimura Kensuke、Zoh Inhae、Jaculbia Rafael B.、Yoshino Hiroko、Muranaka Atsuya、Uchiyama Masanobu、Kim Yousoo
  • Journal Title: Nature Volume: 603 Issue: 7903 Pages: 829-834
  • DOI: 10.1038/s41586-022-04401-0
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Single-molecule laser nanospectroscopy with micro-electron volt energy resolution (2021)
  • Author(s): H. Imada, M. Imai-Imada, K. Miwa, H. Yamane, T. Iwasa, Y. Tanaka, N. Toriumi, K. Kimura, N. Yokoshi, A. Muranaka, M. Uchiyama, T. Taketsugu, Y. K. Kato, H. Ishihara, Y. Kim
  • Journal Title: Science Volume: 373（6550） Issue: 6550 Pages: 95-98
  • DOI: 10.1126/science.abg8790
  • Peer Reviewed
• [Journal Article] Chemical Identification and Bond Control of π-Skeletons in a Coupling Reaction (2021)
  • Author(s): Zhang Chi、Jaculbia Rafael B.、Tanaka Yusuke、Kazuma Emiko、Imada Hiroshi、Hayazawa Norihiko、Muranaka Atsuya、Uchiyama Masanobu、Kim Yousoo
  • Journal Title: Journal of the American Chemical Society Volume: 143 Issue: 25 Pages: 9461-9467
  • DOI: 10.1021/jacs.1c02624
  • Peer Reviewed
• [Journal Article] Synthesis of a Mechanically Planar Chiral and Axially Chiral [2]Rotaxane (2021)
  • Author(s): Tajima Shinya、Muranaka Atsuya、Naito Masaya、Taniguch Noriho、Harada Mei、Miyagawa Shinobu、Ueda Masahiro、Takaya Hikaru、Kobayashi Nagao、Uchiyama Masanobu、Tokunaga Yuji
  • Journal Title: Organic Letters Volume: 23 Issue: 22 Pages: 8678-8682
  • DOI: 10.1021/acs.orglett.1c02983
  • Peer Reviewed
• [Journal Article] Dianion and Dication of Tetracyclopentatetraphenylene as Decoupled Annulene‐within‐an‐Annulene Models (2021)
  • Author(s): Miyoshi Hirokazu、Sugiura Ryosuke、Kishi Ryohei、Spisak Sarah N.、Wei Zheng、Muranaka Atsuya、Uchiyama Masanobu、Kobayashi Nagao、Chatterjee Shreyam、Ie Yutaka、Hisaki Ichiro、Petrukhina Marina A.、Nishinaga Tohru、Nakano Masayoshi、Tobe Yoshito
  • Journal Title: Angewandte Chemie International Edition Volume: 61 Issue: 6 Pages: 1-10
  • DOI: 10.1002/anie.202115316
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Development of Phthalocyanine-Based Functional Molecules with Tunable Optical and Chiroptical Properties (2021)
  • Author(s): Muranaka Atsuya、Uchiyama Masanobu
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 94 Issue: 3 Pages: 872-878
  • DOI: 10.1246/bcsj.20200336
  • NAID: 130008021849
  • Peer Reviewed / Open Access
• [Presentation] Coordination Chemistry of Open-Ring Hemiporphyrazines (2023)
  • Author(s): A. Muranaka
  • Organizer: 243rd ECS Meeting
  • Int'l Joint Research / Invited
• [Presentation] Synthesis and Characterization of Near-infrared Absorbing π-Conjugated Molecules (2023)
  • Author(s): A. Muranaka
  • Organizer: 2023 RIKEN-NCHU Symposium,
  • Int'l Joint Research / Invited
• [Presentation] Synthesis and Chiroptical Properties of Helical Open-Ring Hemiporphyrazines (2022)
  • Author(s): A. Muranaka, X. Ouyang, Y. Tanaka, M. Uchiyama, H. Koshino
  • Organizer: 12th International Conference on Porphyrins and Phthalocyanines
  • Int'l Joint Research / Invited
• [Presentation] 有機色素を扱うための基礎知識と研究紹介 (2021)
  • Author(s): 村中厚哉
  • Organizer: ケムステVシンポ「未来を拓く多彩な色素材料」
  • Invited
• [Presentation] Ring-Opened Hemiporphyrazines: Helical Molecules Exhibiting Circularly Polarized Luminescence (2021)
  • Author(s): A. Muranaka, Y. Tanaka, T. Murayama, E. Imai, M. Uchiyama
  • Organizer: 11th International Conference on Porphyrins and Phthalocyanines
  • Invited
• [Presentation] Development of Phthalocyanine-based Functional Molecules (2021)
  • Author(s): A. Muranaka
  • Organizer: 2021 RIKEN-NCHU Symposium
  • Invited
• [Presentation] フタロシアニン系機能性色素の開発 (2021)
  • Author(s): 村中厚哉
  • Organizer: 2020年度次世代育成研究グループ「高機能性有機色素の開発」講演会（岡山大学）
  • Invited
• [Presentation] 安定キノジメタン系ラジカルカチオンの 光学特性と電気的特性 (2021)
  • Author(s): 原田芽生、谷岡卓、村中厚哉、神野伸一郎、内山 真伸
  • Organizer: 日本薬学会第141年会
• [Book] 未来を拓く多彩な色素材料 (2021)
  • Author(s): 日本化学会
  • Total Pages: 212
  • Publisher: 化学同人
  • ISBN: 9784759814002