Functional Liquids Containing Metal Complexes: Physical Properties, Chemical Reactions, and Structural Functions

• Project/Area Number: 20H02756
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 34010:Inorganic/coordination chemistry-related
• Research Institution: Kobe University
• Principal Investigator: MOCHIDA Tomoyuki 神戸大学, 理学研究科, 教授 (30280580)
• Co-Investigator(Kenkyū-buntansha): 桑原 大介 電気通信大学, 研究設備センター, 准教授 (50270468)
• Project Period (FY): 2020-04-01 – 2024-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥18,200,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥4,200,000); Fiscal Year 2023: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2022: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2021: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2020: ¥10,790,000 (Direct Cost: ¥8,300,000、Indirect Cost: ¥2,490,000)
• Keywords: 金属錯体 / イオン液体

Outline of Research at the Start

金属錯体は種々の機能性を示す物質だが、普通は高融点の固体である。ところが申請者らは、金属錯体をイオン液体化する方法を用いて、多彩な機能性液体を開発してきた。本課題では、こうした金属錯体系液体の研究に、新たに空間の概念を導入し、電子物性、化学反応性、および空間機能の三軸方向に統合展開する。すなわち種々の物性・反応性を有する機能性イオン液体を開発し、それらを用いた空間構築・空間機能開拓を行う。こうして液体と固体を俯瞰した、機能物質科学の新領域を拓く。

Outline of Final Research Achievements

In this study, we developed various ionic liquids from metal complexes and achieved several liquid functionalities by applying basic concepts of coordination chemistry, such as linkage isomerization, ligand exchange, and mixed valence. We also developed photofunctional liquids and gels exhibiting photo-induced ionic conductivity changes, photo-induced material responses, and photoisomerization.

Academic Significance and Societal Importance of the Research Achievements

本研究では、各種の金属錯体をイオン液体化し、その機能性を広範に開拓した。これは、従来は固体化学が中心であった金属錯体研究に対して、液体の視点を導入し、新しい物質科学の分野を開拓するものである。得られた研究成果は、金属錯体の液体研究のさらなる展開可能性を示しており、今後、より多彩な機能物質の開発や、応用的なデバイス研究につながると期待される。

Research Products

• [Journal Article] Thermal properties and bromine addition reaction of ionic liquids containing vinyl-substituted bis-sulfonylamide anion (2024)
  • Author(s): Sumitani Ryo、Nakazono Yosuke、Soga Rio、Mochida Tomoyuki
  • Journal Title: Journal of Molecular Liquids Volume: 397 Pages: 124163-124163
  • DOI: 10.1016/j.molliq.2024.124163
  • Peer Reviewed / Open Access
• [Journal Article] Ionic plastic crystals and ionic liquids containing quaternary cations with alkenyl substituents: chemical phase transformations by bromine vapor (2024)
  • Author(s): Nakazono Yosuke、Inoue Ryota、Sumitani Ryo、Mochida Tomoyuki
  • Journal Title: New Journal of Chemistry Volume: 48 Issue: 5 Pages: 2219-2225
  • DOI: 10.1039/d3nj05633c
  • Peer Reviewed / Open Access
• [Journal Article] Ionic liquids containing half-sandwich ruthenium complexes: in-situ interconversions via photochemical and thermal ligand exchange (2023)
  • Author(s): Mochida Tomoyuki、Maekawa Syou、Sumitani Ryo
  • Journal Title: New Journal of Chemistry Volume: 47 Issue: 41 Pages: 19096-19102
  • DOI: 10.1039/d3nj03953f
  • Peer Reviewed / Open Access
• [Journal Article] Substituent effects on the photoreactivity of Ru-containing ionic liquids exhibiting reversible ionic conductivity changes (2023)
  • Author(s): Mochida Tomoyuki, Shimada Masato, Sumitani Ryo
  • Journal Title: Journal of Molecular Liquids Volume: 381 Pages: 121822-121822
  • DOI: 10.1016/j.molliq.2023.121822
  • Peer Reviewed / Open Access
• [Journal Article] Organometallic Ionic Liquids Containing Sandwich Complexes: Molecular Design, Physical Properties, and Chemical Reactivities (2023)
  • Author(s): Mochida Tomoyuki
  • Journal Title: The Chemical Record Volume: 23 Issue: 8
  • DOI: 10.1002/tcr.202300041
  • Peer Reviewed / Open Access
• [Journal Article] Structures, Thermal Properties, and Reactivities of Cationic Rh-cod Complexes in Solid State (cod = 1,5-Cyclooctadiene) (2023)
  • Author(s): Sumitani Ryo, Kuwahara Daisuke, Mochida Tomoyuki
  • Journal Title: Inorganic Chemistry Volume: 62 Issue: 5 Pages: 2169-2180
  • DOI: 10.1021/acs.inorgchem.2c03865
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and Electrochemical Properties of Mixed‐Metal Triangular Complexes Based on Ferrocene‐Based Ligands and Dinuclear Arene Ruthenium Building Blocks (2022)
  • Author(s): Horikoshi Ryo、Sumitani Ryo、Shimooka Natsuko、Mochida Tomoyuki
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2022 Issue: 33
  • DOI: 10.1002/ejic.202200453
  • Peer Reviewed / Open Access
• [Journal Article] Thermal Properties and Solvent Polarities of Mixed-Valence Ionic Liquids Containing Cationic Biferrocenylene Derivatives (2022)
  • Author(s): Hamada Shota、Mochida Tomoyuki
  • Journal Title: Inorganic Chemistry Volume: 61 Issue: 21 Pages: 8160-8167
  • DOI: 10.1021/acs.inorgchem.2c00395
  • Peer Reviewed / Open Access
• [Journal Article] On-demand gelation of ionic liquids using photoresponsive organometallic gelators (2022)
  • Author(s): Ryo Sumitani, Masamichi Yamanaka, Tomoyuki Mochida
  • Journal Title: Soft Matter Volume: － Issue: 18 Pages: 3479-3486
  • DOI: 10.1039/d2sm00307d
  • Peer Reviewed / Open Access
• [Journal Article] Thermal properties, crystal structures, and photoreactivity of Ru-containing ionic liquids with sulfur-containing substituents (2021)
  • Author(s): Ryo Sumitani, Tomoyuki Mochida
  • Journal Title: Journal of Molecular Liquids Volume: 344 Pages: 117784-117784
  • DOI: 10.1016/j.molliq.2021.117784
  • Peer Reviewed / Open Access
• [Journal Article] Switchable ionic conductivity and viscoelasticity of ionogels containing photo- and thermo-responsive organometallic ionic liquids (2021)
  • Author(s): Ryo Sumitani, Tomoyuki Mochida
  • Journal Title: Journal of Molecular Liquids Volume: 342 Pages: 117510-117510
  • DOI: 10.1016/j.molliq.2021.117510
  • Peer Reviewed / Open Access
• [Journal Article] Anion-Ordering Phase Transitions in Biferrocenium and Ferrocenium Salts with the Bis(trifluoromethanesulfonyl)amide Anion (2021)
  • Author(s): Kimata Hironori、Inagaki Takashi、Mochida Tomoyuki
  • Journal Title: ACS Omega Volume: 6 Issue: 32 Pages: 21139-21146
  • DOI: 10.1021/acsomega.1c03059
  • NAID: 120007159895
  • Peer Reviewed / Open Access
• [Journal Article] Photoinduced and Thermal Linkage Isomerizations of an Organometallic Ionic Liquid Containing a Half-Sandwich Ruthenium Thiocyanate Complex (2021)
  • Author(s): Mochida Tomoyuki、Maekawa Syou、Sumitani Ryo
  • Journal Title: Inorganic Chemistry Volume: 60 Issue: 16 Pages: 12386-12391
  • DOI: 10.1021/acs.inorgchem.1c01613
  • Peer Reviewed / Open Access
• [Journal Article] Luminescent Rhenium-containing Ionic Liquid Exhibiting Photoinduced Vapochromism (2021)
  • Author(s): Cho Sok-Yong、Mochida Tomoyuki
  • Journal Title: Chemistry Letters Volume: 50 Issue: 10 Pages: 1740-1742
  • DOI: 10.1246/cl.210386
  • NAID: 130008101931
  • Peer Reviewed / Open Access
• [Journal Article] Nitro-Nitrito Photoisomerization of Cationic Platinum(II) Complexes in the Solid State: Reactivity in Polymorphic Crystals and Glassy State (2021)
  • Author(s): Nakamura Ibuki、Sumitani Ryo、Mochida Tomoyuki
  • Journal Title: Crystal Growth & Design Volume: 21 Issue: 3 Pages: 1861-1868
  • DOI: 10.1021/acs.cgd.1c00004
  • NAID: 120007028962
  • Peer Reviewed / Open Access
• [Journal Article] Thermal properties, crystal structures, and phase diagrams of ionic plastic crystals and ionic liquids containing a chiral cationic sandwich complex (2020)
  • Author(s): Mochida Tomoyuki、Sumitani Ryo、Yamazoe Tomoaki
  • Journal Title: Physical Chemistry Chemical Physics Volume: 22 Issue: 44 Pages: 25803-25810
  • DOI: 10.1039/d0cp04870d
  • NAID: 120006938922
  • Peer Reviewed / Open Access
• [Journal Article] Nitro-Nitrito Photoisomerization of Platinum(II) Complexes with Pt(NO2)4 2- and (FSO2)2N- Anions: Correlation between Isomerization Ratio and Reaction Cavity (2020)
  • Author(s): Nakamura Ibuki、Funasako Yusuke、Mochida Tomoyuki
  • Journal Title: Crystal Growth & Design Volume: 20 Issue: 12 Pages: 8047-8052
  • DOI: 10.1021/acs.cgd.0c01294
  • NAID: 120006952744
  • Peer Reviewed / Open Access
• [Journal Article] Reversible formation of soft coordination polymers from liquid mixtures of photoreactive organometallic ionic liquid and bridging molecules (2020)
  • Author(s): Sumitani Ryo、Mochida Tomoyuki
  • Journal Title: Soft Matter Volume: 16 Issue: 43 Pages: 9946-9954
  • DOI: 10.1039/d0sm01567a
  • NAID: 120006919982
  • Peer Reviewed / Open Access
• [Journal Article] Thermal properties and crystal structures of ruthenium-containing photoreactive ionic liquids with short substituents (2020)
  • Author(s): Sumitani Ryo、Funasako Yusuke、Mochida Tomoyuki
  • Journal Title: Journal of Molecular Liquids Volume: 318 Pages: 114071-114071
  • DOI: 10.1016/j.molliq.2020.114071
  • NAID: 120006952745
  • Peer Reviewed / Open Access
• [Journal Article] Metal-Containing Poly(ionic liquid) Exhibiting Photogeneration of Coordination Network: Reversible Control of Viscoelasticity and Ionic Conductivity (2020)
  • Author(s): Sumitani Ryo、Mochida Tomoyuki
  • Journal Title: Macromolecules Volume: 53 Issue: 16 Pages: 6968-6974
  • DOI: 10.1021/acs.macromol.0c01141
  • NAID: 120006886644
  • Peer Reviewed / Open Access
• [Journal Article] Reversible Control of Ionic Conductivity and Viscoelasticity of Organometallic Ionic Liquids by Application of Light and Heat (2020)
  • Author(s): Ryo Sumitani, Hirofumi Yoshikawa and Tomoyuki Mochida
  • Journal Title: Chem. Commun. Volume: 56 Issue: 46 Pages: 6189-6192
  • DOI: 10.1039/d0cc02786c
  • NAID: 120006867368
  • Peer Reviewed / Open Access
• [Presentation] 二重結合を有するイオン液体の臭素付加反応および双性イオン形成反応 (2023)
  • Author(s): 中園陽介, 角谷凌, 持田智行
  • Organizer: 第13回イオン液体討論会
• [Presentation] 金属錯体からなるイオン液体の多彩な機能性 (2023)
  • Author(s): 持田智行
  • Organizer: 第54回中部化学関係学協会支部連合秋季大会
  • Invited
• [Presentation] 二重結合を有する四級塩における結晶相・柔粘性結晶相・液相間の化学的相転換 (2023)
  • Author(s): 中園陽介, 井上亮汰, 角谷凌, 持田智行
  • Organizer: 第31回有機結晶シンポジウム
• [Presentation] 金属錯体で創る多彩な機能性イオン液体 (2023)
  • Author(s): 持田智行
  • Organizer: 日本分析化学会 第72年会
  • Invited
• [Presentation] Phase Behaviors and Reactivities of Ionic Crystals Containing Cationic Rh-cod Complexes (2022)
  • Author(s): 角谷凌, 持田智行, 桑原大介
  • Organizer: 第12回イオン液体討論会
• [Presentation] 光でゲル化剤を放出するルテニウム錯体の開発：イオン液体ゲルの可逆形成 (2022)
  • Author(s): 角谷凌, 持田智行, 山中正道
  • Organizer: 第33回配位化合物の光化学討論会 (オンライン開催）
• [Presentation] Photo-Controlled Gelation of Ionic Liquids Using Gelator-Coordinated Ruthenium Complexes (2022)
  • Author(s): R. Sumitani, T. Mochida, M. Yamanaka
  • Organizer: 8th Asian Conference on Coordination Chemistry (Hybrid Conference)
  • Int'l Joint Research
• [Presentation] サンドイッチ型Rh錯体をカチオンとするイオン結晶の相挙動 (2022)
  • Author(s): 角谷凌, 持田智行
  • Organizer: 日本化学会第102春季年会
• [Presentation] 含フェロセン配位子とルテニウム二核錯体からなる三角形三核錯体の合成と構造 (2022)
  • Author(s): 堀越亮, 角谷凌, 持田智行
  • Organizer: 日本化学会第102春季年会
• [Presentation] Gelator-Coordinated Organometallic Ionic Liquids for Photo-Controlled Gelation of Liquids (2021)
  • Author(s): 角谷凌, 持田智行, 山中正道
  • Organizer: 第11回イオン液体討論会
• [Presentation] Effects of Substituents on the Photoreactivity of Ionic Liquids Containing Ruthenium Complexes (2021)
  • Author(s): 島田壮人, 角谷凌, 山添智暉, 持田智行
  • Organizer: 第11回イオン液体討論会
• [Presentation] Reversible Formation of Ionic Liquid Gels Through Photochemical Reaction of Gelator-Coordinated Ruthenium Complexes (2021)
  • Author(s): 角谷凌, 持田智行, 山中正道
  • Organizer: 錯体化学会第71回討論会
• [Presentation] イオン伝導度を外場制御できるルテニウム錯体含有ソフトマターの開発 (2021)
  • Author(s): 角谷凌, 持田智行
  • Organizer: 第32回配位化合物の光化学討論会
• [Presentation] Ruthenium-Containing Ionic Liquid Gels Exhibiting Ionic Conductivity Changes in Response to External Stimuli (2021)
  • Author(s): R. Sumitani, T. Mochida
  • Organizer: 6th Iberoamerican Meeting on Ionic Liquids
  • Int'l Joint Research
• [Presentation] Ionogels containing ruthenium-complexes and exhibiting ionic conductivity changes by application of external stimuli (2021)
  • Author(s): 角谷凌, 持田智行
  • Organizer: 日本化学会第101春季年会
• [Presentation] 結合異性化を起こすルテニウム錯体含有イオン液体の合成 (2021)
  • Author(s): 前川翔, 持田智行
  • Organizer: 日本化学会第101春季年会
• [Presentation] Photoreactive Ionogels Containing Organometallic Ruthenium Complexes (2020)
  • Author(s): 角谷凌, 持田智行
  • Organizer: イオン液体Workshop2020
• [Presentation] イオン伝導度を光と熱でスイッチングできる金属錯体含有イオン液体 (2020)
  • Author(s): 角谷凌, 持田智行
  • Organizer: 第10回CSJ化学フェスタ2020
• [Presentation] 光と熱でイオン伝導度を可逆制御できるルテニウム錯体系イオン液体 (2020)
  • Author(s): 角谷凌, 持田智行
  • Organizer: 第9回 JACI/GSCシンポジウム