Liquid-crystalline nano space as novel reaction fields

• Project/Area Number: 19H00902
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
• Research Institution: Nagoya University
• Principal Investigator: Tanaka Kentaro 名古屋大学, 理学研究科, 教授 (40281589)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥45,890,000 (Direct Cost: ¥35,300,000、Indirect Cost: ¥10,590,000); Fiscal Year 2021: ¥13,260,000 (Direct Cost: ¥10,200,000、Indirect Cost: ¥3,060,000); Fiscal Year 2020: ¥13,260,000 (Direct Cost: ¥10,200,000、Indirect Cost: ¥3,060,000); Fiscal Year 2019: ¥19,370,000 (Direct Cost: ¥14,900,000、Indirect Cost: ¥4,470,000)
• Keywords: 液晶 / 分子組織 / 大環状化合物 / 分子認識 / 自己組織化 / 金属錯体 / 超分子 / 大環状分子 / 自己集合 / カラムナ組織 / 配向組織化 / ナノ空間 / 反応場

Outline of Research at the Start

本研究では、液晶の中に構築したナノ空間を利用した、今までに例を見ない反応場を構築する。我々は、カラムナー液晶性の大環状大環状化合物を作ることで、分子を内包できるナノ空間を液体の中に創り出すことに成功してきた。反応媒体として大環状カラムナー液晶のナノ空間を用いることは、液晶性ナノ空間に反応基質分子を集積・配向することを意味し、空間が規定する精密選択的合成への展開が期待できる。本研究では、この新しいナノ空間を最大限に活用し、様々な新しい反応と、それにより得られる機能物質構築を行う。

Outline of Final Research Achievements

The aim of this study was generation of liquid-crystalline nano spaces which can accommodate guest molecules and to use the nano spaces for novel reaction media. We have obtained the research findings listed below. 1) Invention of novel liquid crystals of macrocyclic mesogens and metallo-foldamer mesogens. 2) Confirmation of presence of the nano spaces in the liquid crystals and the ability of accommodation of guest moelcules. 3) Application of the liquid-crystalline macrocycles to construction of functional molecular arrays.

Academic Significance and Societal Importance of the Research Achievements

本研究は、化学的構造が明確な大環状化合物から、液晶の中に分子を導入可能な分子ナノ空間を作る方法論を構築した。このナノ空間は、ディスクリートかつ一義的なサイズや形状を持つため、新しい化学反応、特に一義的な物質合成のためのテンプレートを作る上で有用である。

Research Products

• [Journal Article] Direct catalytic benzene hydroxylation under mild reaction conditions by using a monocationic μ-nitrido-bridged iron phthalocyanine dimer with 16 peripheral methyl groups (2022)
  • Author(s): Yamada Yasuyuki、Teoh Chee-Ming、Toyoda Yuka、Tanaka Kentaro
  • Journal Title: New Journal of Chemistry Volume: 46 Issue: 3 Pages: 955-958
  • DOI: 10.1039/d1nj05369h
  • Peer Reviewed
• [Journal Article] Mesogenic discrete metallofoldamer for columnar liquid crystal (2022)
  • Author(s): Kawano Shin-ichiro、Narita Kazutaka、Ikemoto Yuka、Sasaki Ako、Tanaka Kentaro
  • Journal Title: Chemical Communications Volume: 58 Issue: 20 Pages: 3274-3277
  • DOI: 10.1039/d2cc00310d
  • Peer Reviewed
• [Journal Article] Thermally Stable Array of Discrete C₆₀s on a Two-Dimensional Crystalline Adlayer of Macrocycles both in Vacuo and under Ambient Pressure (2022)
  • Author(s): Kawano Shin-ichiro、Nakaya Masato、Saitow Masaaki、Ishiguro Atsuki、Yanai Takeshi、Onoe Jun、Tanaka Kentaro
  • Journal Title: Journal of the American Chemical Society Volume: 144 Issue: 15 Pages: 6749-6758
  • DOI: 10.1021/jacs.1c13610
  • Peer Reviewed
• [Journal Article] Significant Effect of Flexibility of Bridging Alkyl Chains on?the?Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with Fourfold Rotaxane Linkage (2022)
  • Author(s): Yamada Yasuyuki、Iida Hayato、Shibano Shinya、Mihara Nozomi、Kato Tatsuhisa、Tanaka Kentaro
  • Journal Title: Chemistry - A European Journal Volume: 28 Issue: 37
  • DOI: 10.1002/chem.202200819
  • Peer Reviewed
• [Journal Article] Synthesis of bis{meso-tetrakis(4-N-alkylpyridiniumyl) porphyrinato}cerium and Its Redox Switching Behavior (2021)
  • Author(s): Toshio Nishino, Yasuyuki Yamada, Ayumi Yamamoto, Kentaro Tanaka
  • Journal Title: Molecules Volume: 26 Issue: 4 Pages: 790-790
  • DOI: 10.3390/molecules26040790
  • Peer Reviewed / Open Access
• [Journal Article] High catalytic methane oxidation activity of monocationic μ-nitrido-bridged iron phthalocyanine dimer with sixteen methyl groups (2021)
  • Author(s): Yamada Yasuyuki、Kura Jyunichi、Toyoda Yuka、Tanaka Kentaro
  • Journal Title: Dalton Transactions Volume: 50 Issue: 19 Pages: 6718-6724
  • DOI: 10.1039/d1dt00941a
  • Peer Reviewed
• [Journal Article] Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity (2021)
  • Author(s): Yamada Yasuyuki、Miwa Yusuke、Toyoda Yuka、Yamaguchi Tomoo、Akine Shigehisa、Tanaka Kentaro
  • Journal Title: Dalton Transactions Volume: 50 Issue: 45 Pages: 16775-16781
  • DOI: 10.1039/d1dt02922c
  • Peer Reviewed
• [Journal Article] Metalloporphyrins substituted with N-carbazolyl groups quadruply at meso positions (2021)
  • Author(s): Kawano Shin-ichiro、Kawada Sae、Matsubuchi Atsuya、Tanaka Kentaro
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 26 Issue: 02 Pages: 140-146
  • DOI: 10.1142/s1088424621501170
  • Peer Reviewed
• [Journal Article] 巨大環状化合物をメソゲンとしたカラムナー液晶による流動性ナノ空間の構築 (2021)
  • Author(s): 河野慎一郎、田中健太郎
  • Journal Title: 液晶 Volume: 25 Pages: 40-45
  • Peer Reviewed
• [Journal Article] Development of functional molecular assemblies based on programmable construction of face-to-face assemblies of metallo-porphyrinoids (2020)
  • Author(s): Yamada Yasuyuki、Tanaka Kentaro
  • Journal Title: Journal of Inclusion Phenomena and Macrocyclic Chemistry Volume: 96 Issue: 3-4 Pages: 197-213
  • DOI: 10.1007/s10847-019-00969-9
  • Peer Reviewed
• [Journal Article] Structure and dynamics of a chiral cubanoid complex composed of lithium and salphen (2020)
  • Author(s): Kawano Shin-ichiro、Tomita Kyohei、Tanaka Kentaro
  • Journal Title: Inorganica Chimica Acta Volume: 512 Pages: 119894-119894
  • DOI: 10.1016/j.ica.2020.119894
  • Peer Reviewed
• [Journal Article] μ-Nitrido-bridged iron phthalocyanine dimer bearing eight peripheral 12-crown-4 units and its methane oxidation activity (2020)
  • Author(s): Yamada Yasuyuki、Kura Jyunichi、Toyoda Yuka、Tanaka Kentaro
  • Journal Title: New Journal of Chemistry Volume: 44 Issue: 44 Pages: 19179-19183
  • DOI: 10.1039/d0nj04601a
  • Peer Reviewed
• [Journal Article] Improved Synthesis of Monocationic myu-Nitrido-Bridged Iron Phthalocyanine Dimer with No Peripheral Substituents (2019)
  • Author(s): Y. Yamada, T. Sugiura, H. Ariga-Miwa, K. Morita, and K. Tanaka
  • Journal Title: Inorg. Chimica Acta Volume: 489 Pages: 160-163
  • Peer Reviewed
• [Journal Article] Catalytic methane oxidation by a supramolecular conjugate based on a μ-nitrido-bridged iron porphyrinoid dimer (2019)
  • Author(s): Y. Yamada, K. Morita, N. Mihara, K. Igawa, K. Tomooka and K. Tanaka
  • Journal Title: New J. Chem. Volume: 43 Issue: 29 Pages: 11477-11482
  • DOI: 10.1039/c9nj02210d
  • Peer Reviewed
• [Journal Article] Liquid‐crystalline Metallomacrocycles Composed of Bis(hydroxypyridono)toluene Ligand and Cu 2+ Ions (2019)
  • Author(s): Kawano Shin‐ichiro、Ideta Kohei、Banno Tomohiko、Tanaka Kentaro
  • Journal Title: Chemistry - An Asian Journal Volume: 14 Issue: 23 Pages: 4415-4419
  • DOI: 10.1002/asia.201901323
  • Peer Reviewed
• [Presentation] 8つのコラニュレンをもつ大環状金属錯体型分子レセプターに よるフラーレンの包接 (2022)
  • Author(s): 小林 侑太・河野 慎一郎・田中 健太郎
  • Organizer: 日本化学会第102春季年会
• [Presentation] Host-Guest Chemistry of Porphyrins in Liquid Crystalline Macrocycles (2021)
  • Author(s): K. Tanaka
  • Organizer: 239th ECS Meeting
  • Int'l Joint Research / Invited
• [Presentation] Switchable Supramolecular Conjugates Composed of Porphyrin and Phthalocyanine (2021)
  • Author(s): K. Tanaka
  • Organizer: 11th International Conference on Porphyrins and Phthalocyanines (ICPP-11)
  • Int'l Joint Research / Invited
• [Presentation] ナノポーラス液晶 (2021)
  • Author(s): 田中健太郎
  • Organizer: 電気学会光・量子デバイス研究会「革新的材料の創出とデバイス応用」
  • Invited
• [Presentation] 新規なμ-窒素架橋鉄ポルフィセン二量体の合成とそのメタン酸化活性 (2021)
  • Author(s): 三輪祐介, 山田泰之, 豊田由香, 山口智雄, 田中健太郎
  • Organizer: 第71回錯体化学会討論会
• [Presentation] 4つの[3]ロタキサン側鎖を持つテルビウム(III)フタロシアニンダブルデッカー錯体の合成 (2021)
  • Author(s): 山田遙香, 西川敦基, 小林千紗, 山田泰之, 田中健太郎
  • Organizer: 第18回ホスト－ゲスト・超分子化学シンポジウム
• [Presentation] 超分子的フラーレン組織化 (2021)
  • Author(s): 小林侑太、河野真一郎、田中健太郎
  • Organizer: 第6回 D-マテリアルズ分野融合研究会
• [Presentation] 超分子的相互作用による単分子磁石の物性制御 (2021)
  • Author(s): 山田遥香、山田泰之、田中健太郎
  • Organizer: 第6回 D-マテリアルズ分野融合研究会
• [Presentation] 高反応性メタン酸化触媒の開発 〜窒素架橋鉄ポルフィセン二量体の合成と触媒活性〜 (2021)
  • Author(s): 三輪祐介、山田 泰之、田中健太郎
  • Organizer: 第6回 D-マテリアルズ分野融合研究会
• [Presentation] Moleular Capturing in Liquid Crystals, Two Dimensional Crystals and Cages Composed of Macrocycles (2021)
  • Author(s): Kentaro Tanaka
  • Organizer: 2020 Dalian University of Technology- Overseas Partner Universities Series Online Exchange Conference
  • Int'l Joint Research / Invited
• [Presentation] 129Xe NMR Structural Analysis of Continuous Porosity of Columnar Liquid Crystal Composed of Stacked Macrocycles (2021)
  • Author(s): Shin-ichiro Kawano, Takahiro Taki, Hiroaki Yoshimizu, Kentaro Tanaka
  • Organizer: 日本化学会第101春季年会
• [Presentation] テトラ(N－カルバゾリル)ポルフィリンを基にした含窒素π拡張ポルフィリンの合成とその電子構造 (2021)
  • Author(s): 松渕 敦也・河野 慎一郎・田中 健太郎
  • Organizer: 日本化学会第101春季年会
• [Presentation] 8つのコラニュレンをもつ大環状金属錯体型フラーレンレセプター (2021)
  • Author(s): 小林 侑太・河野 慎一郎・田中 健太郎
  • Organizer: 日本化学会第101春季年会
• [Presentation] A metallomacrocycle tethering eight corannulenes and the host-guest interaction with C60 (2021)
  • Author(s): Yuta Kobayashi, Shin-ichiro Kawano, Kentaro Tanaka
  • Organizer: The 4th IRCCS International Symposium: 'Multidimensional control over material structure and function'
• [Presentation] リチウムイオンを内包したカラムナー 液晶性大環状化合物の配向制御 (2020)
  • Author(s): 河野慎一郎、冨田恭平、吉尾正史、田中健太郎
  • Organizer: 2020年日本液晶学会オンライン研究発表会
• [Presentation] メソ位をカルバゾールで修飾したポル フィリンを基にした縮環型p拡張ポルフィリンの合成とその電子構造 (2020)
  • Author(s): 松渕 敦也・河野 慎一郎・田中 健太郎
  • Organizer: 錯体化学会 第70回討論会
• [Presentation] Switchable Supramolecular Conjugates of Porphyrin and Phthalocyanine (2020)
  • Author(s): Kentaro Tanaka
  • Organizer: Mini-symposium on Advanced Nanomaterials in Strasbourg
  • Int'l Joint Research / Invited
• [Presentation] Dynamic Molecular Invasion into Multiply Interlocked Catenane Composed of Porphyrins and Phthalocyanine (2019)
  • Author(s): Kentaro Tanaka
  • Organizer: 235th ECS Meeting
  • Int'l Joint Research / Invited
• [Presentation] Host-Guest Chemistry for Arraying Porphyrins (2019)
  • Author(s): Kentaro Tanaka
  • Organizer: 1st Asian Conference on Porphyrins and Phthalocyanines
  • Int'l Joint Research / Invited
• [Presentation] Molecular Capturing by Liquid Crystals, Two dimensional Crystals and Cages composed of Macrocycles (2019)
  • Author(s): Kentaro Tanaka
  • Organizer: 12th China‐Japan Joint Symposium on Metal Cluster Compounds (CJJSMCC2019)
  • Int'l Joint Research / Invited
• [Presentation] Molecular Capturing by Liquid Crystals, Two dimensional Crystals and Cages composed of Macrocycles (2019)
  • Author(s): Kentaro Tanaka
  • Organizer: China‐Japan Joint Interdisciplinary Symposium on Molecular Magnetic Materials
  • Int'l Joint Research / Invited