Development of external-responsive soft crystals using the properties of silicon-silicon bond

• Project Area: Soft Crystals: Science and Photofunctions of Easy-Responsive Systems with Felxibility and Higher-Ordering
• Project/Area Number: 17H06369
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The University of Tokyo
• Principal Investigator: Yamanoi Yoshinori 東京大学, 大学院理学系研究科(理学部), 准教授 (20342636)
• Project Period (FY): 2017-06-30 – 2022-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥39,650,000 (Direct Cost: ¥30,500,000、Indirect Cost: ¥9,150,000); Fiscal Year 2021: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000); Fiscal Year 2020: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000); Fiscal Year 2019: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000); Fiscal Year 2018: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000); Fiscal Year 2017: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000)
• Keywords: ジシラン結合 / ケイ素 / 外部刺激応答性 / CP/MAS NMR / ジシラン / 発光 / SHG / 結晶構造 / 外部刺激 / 相転移 / サーモサリエント現象 / サーモサリエント / 蛍光

Outline of Final Research Achievements

Aromatic disilanes are expected to change their structure and physical properties in conjunction with a weak external stimulus due to the flexibility of the Si-Si single bond and the extension of the conjugated chain due to σ-π conjugation. In this study, we investigated the structural and photophysical properties of cyclic and linear aromatic disilanes induced by external stimuli and theoretical considerations. Specifically, we found mechanochromic luminescence, laser wavelength conversion, and thermosalient phenomena.

Academic Significance and Societal Importance of the Research Achievements

本研究では、我々が開発した手法で芳香族オリゴシラン類を効率良く合成し、外部刺激による構造変化や光物性変化を調査した。すでに様々な有機ケイ素化合物の合成と光物性の研究で有用な結果を得ており、研究期間内に当初計画の大半を達成した。様々な共同研究を通し、本研究課題を遂行することによって、ソフトクリスタルの分野で貢献できた。

Research Products

• [Journal Article] Reversible Transition between Discrete and 1D Infinite Architectures: a Temperature-Responsive Cu(I) Complex with a Flexible Disilane-bridged Bis(pyridine) Ligand (2023)
  • Author(s): Zhao, Y.; Nakae, T.; Takeya, S.; Hattori, M.; Saito, D.; Kato, M.; Ohmasa, Y.; Sato, S.; Yamamuro, O.; Galica, T.; Nishibori, E.; Kobayashi, S.; Seki, T.; Yamada, T.; Yamanoi, Y.*
  • Journal Title: Chem. Eur. J. Volume: 29 Issue: 38
  • DOI: 10.1002/chem.202204002
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] 15N CP/MAS NMR as a Tool for the Mechanistic Study of Mechanical Stimuli-Responsive Materials: Evidence for the Conformational Change of an Emissive Dimethylacridane Derivative (2023)
  • Author(s): Nakae, T.; Hattori, M.; Yamanoi, Y.
  • Journal Title: ACS Omega Volume: 8 Pages: 12922-12927
  • Peer Reviewed / Open Access
• [Journal Article] Thermosalience in macrocycle-based soft crystals via anisotropic deformation of disilanyl architecture (2020)
  • Author(s): Omoto, K.; Nakae, T.; Nishio, M.; Yamanoi, Y.;* Kasai, H.; Nishibori, E.; Mashimo, T.; Seki, T.; Ito, H.; Nakamura, K.; Kobayashi, N.; Nishihara, H.*
  • Journal Title: J. Am. Chem. Soc. Volume: 142 Issue: 29 Pages: 12651-12657
  • DOI: 10.1021/jacs.0c03643
  • Peer Reviewed / Open Access
• [Journal Article] Effect of Tris(trimethylsilyl)silyl Group on the Fluorescence and Triplet Yields of Oligothiophenes (2020)
  • Author(s): Hirata, S.;* Nishio, M.; Uchida, H.; Usuki, T.; Nakae, T.; Miyachi, M.; Yamanoi, Y.;* Nishihara, H.*
  • Journal Title: J. Phys. Chem. C Volume: 124 Issue: 5 Pages: 3277-3286
  • DOI: 10.1021/acs.jpcc.9b10718
  • Peer Reviewed
• [Journal Article] Photoelectric Conversion System Composed of Gene-Recombined Photosystem I and Platinum Nanoparticle Nanosheet (2020)
  • Author(s): Zhu Wenchao、Salles Raphal、Miyachi Mariko、Yamanoi Yoshinori、Tomo Tatsuya、Takahashi Hiromi、Nishihara Hiroshi
  • Journal Title: Langmuir Volume: 36 Issue: 23 Pages: 6429-6435
  • DOI: 10.1021/acs.langmuir.0c00647
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Selective Formation and SHG Intensity of Noncentrosymmetric and Centrosymmetric 1,1,2,2-Tetramethyl-1-(4-(N,N-dimethylamino)phenyl)-2-(2′-cyanophenyl)disilane Crystals under External Stimuli (2020)
  • Author(s): Nishio Masaki、Shimada Masaki、Omoto Kenichiro、Nakae Toyotaka、Maeda Hiroaki、Miyachi Mariko、Yamanoi Yoshinori、Nishibori Eiji、Nakayama Naofumi、Goto Hitoshi、Matsushita Tomonori、Kondo Takashi、Hattori Mineyuki、Jimura Keiko、Hayashi Shigenobu、Nishihara Hiroshi
  • Journal Title: The Journal of Physical Chemistry C Volume: 124 Issue: 32 Pages: 17450-17458
  • DOI: 10.1021/acs.jpcc.0c03139
  • Peer Reviewed / Open Access
• [Journal Article] Photosensing system using photosystem I and gold nanoparticle on graphene field-effect transistor (2019)
  • Author(s): Nishiori, D.; Zhu, W.; Salles, R.; Miyachi, M.;* Yamanoi, Y.;* Ikuta, T.; Maehashi, K.; Tomo, T.; Nishihara, H.*
  • Journal Title: ACS Appl. Mater. Inter. Volume: 11 Issue: 45 Pages: 42773-42779
  • DOI: 10.1021/acsami.9b14771
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Enhancement of Photofunction of Phosphorescent Pt(II) Cyclometalated Complexes Driven by Substituents: Solid-state Luminescence and Circularly Polarized Luminescence (2019)
  • Author(s): Usuki, T.; Uchida, H.; Omoto, K.; Yamanoi, Y.;* Yamada, A.; Iwamura, M.; Nozaki, K.; Nishihara, H.*
  • Journal Title: J. Org. Chem. Volume: 84 Issue: 17 Pages: 10749-10756
  • DOI: 10.1021/acs.joc.9b01285
  • Peer Reviewed
• [Journal Article] Dioxacyclophanes as a Scaffold for Silicon-based Circularly Polarized Luminescent Materials (2019)
  • Author(s): Yamanoi, Y.;* Usuki, T.; Omoto, K.; Shimada, M.; Koike, H.; Iwamura, M.; Nozaki, K.; Saito, D.;
  • Journal Title: Tetrahedron Lett. Volume: 60 Issue: 16 Pages: 1108-1112
  • DOI: 10.1016/j.tetlet.2019.03.033
  • Peer Reviewed
• [Journal Article] Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor-Acceptor-Donor Triads (2019)
  • Author(s): Usuki Tsukasa、Omoto Kenichiro、Shimada Masaki、Yamanoi Yoshinori、Kasai Hidetaka、Nishibori Eiji、Nishihara Hiroshi
  • Journal Title: Molecules Volume: 24 Issue: 3 Pages: 521-521
  • DOI: 10.3390/molecules24030521
  • NAID: 120007128246
  • Peer Reviewed / Open Access
• [Journal Article] 芳香族ケイ素化合物の新規合成プロセスの開拓と固体光物性 (2019)
  • Author(s): 山野井 慶徳
  • Journal Title: 化学工業 Volume: 4 Pages: 12-18
• [Journal Article] Aggregation-Induced Emission Enhancement from Disilane-Bridged Donor-Acceptor-Donor Luminogens Based on the Triarylamine Functionality (2018)
  • Author(s): Usuki Tsukasa、Shimada Masaki、Yamanoi Yoshinori、Ohto Tatsuhiko、Tada Hirokazu、Kasai Hidetaka、Nishibori Eiji、Nishihara Hiroshi
  • Journal Title: ACS Appl. Mater. Interfaces Volume: in press Issue: 15 Pages: 12164-12172
  • DOI: 10.1021/acsami.7b14802
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Attachment chemistry of aromatic compounds on a Silicon(100) surface (2018)
  • Author(s): Henriksson Anders、Nishiori Daiki、Maeda Hiroaki、Miyachi Mariko、Yamanoi Yoshinori、Nishihara Hiroshi
  • Journal Title: Surface Science Volume: 669 Pages: 140-144
  • DOI: 10.1016/j.susc.2017.11.017
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 固体状態で強く発光する有機ケイ素化合物 (2018)
  • Author(s): 山野井 慶徳
  • Journal Title: ケイ素化学協会誌 Volume: 35 Pages: 11-17
  • Peer Reviewed
• [Journal Article] 分子アーキテクトニクスの化学：電子部品と分子構造 (2018)
  • Author(s): 山野井 慶徳，西原 寛
  • Journal Title: 「CSJカレントレビュー 分子アーキテクトニクス」 Volume: 2018 Pages: 22-29
  • Peer Reviewed
• [Journal Article] Multifunctional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence (2017)
  • Author(s): Shimada Masaki、Yamanoi Yoshinori、Ohto Tatsuhiko、Pham Song-Toan、Yamada Ryo、Tada Hirokazu、Omoto Kenichiro、Tashiro Shohei、Shionoya Mitsuhiko、Hattori Mineyuki、Jimura Keiko、Hayashi Shigenobu、Koike Hikaru、Iwamura Munetaka、Nozaki Koichi、Nishihara Hiroshi
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 32 Pages: 11214-11221
  • DOI: 10.1021/jacs.7b05671
  • Peer Reviewed
• [Journal Article] Modification of Electrode Interfaces with Nanosized Materials for Electronic Applications” (2017)
  • Author(s): Yamanoi, Y.; Miyachi, M.; Nishihara, H.
  • Journal Title: Molecular Architectonics: The Third Stage of Single Molecule Electronics, Volume: 2017 Pages: 399-416
• [Journal Article] 光応答素子のための光化学系Iとカーボンナノチューブの複合体形成 (2017)
  • Author(s): 二井 大輔，宮地 麻里子，嶋田 友一郎，野沢 陽佑，伊藤 雅浩，本間 芳和，池平 秀，山野井 慶徳，西原 寛，鞆 達也
  • Journal Title: 光合成研究 News letter Volume: 27 Pages: 22-31
  • Peer Reviewed
• [Presentation] 山野井 慶徳 (2021)
  • Author(s): 外部刺激で光物性が変化する直鎖状芳香族ジシラン分子の開発
  • Organizer: 新学術領域研究「ソフトクリスタル」 第7回公開シンポジウム
• [Presentation] シアノバクテリアの光化学系Iを活用した電極の作製と物性評価 (2020)
  • Author(s): 山野井 慶徳，
  • Organizer: 日本板硝子材料工学助成会 第37回無機材料に関する最近の研究成果発表会－材料研究に新しい風を－
  • Invited
• [Presentation] 「ジシラン結合の柔軟性に基づくソフトクリスタル」 (2020)
  • Author(s): 山野井 慶徳
  • Organizer: 新学術領域研究「ソフトクリスタル」 第5回公開シンポジウム
  • Invited
• [Presentation] 「シアノバクテリアの光化学系Iを活用した電極の作製と物性評価」 (2020)
  • Author(s): 山野井 慶徳
  • Organizer: 日本板硝子材料工学助成会 第37回無機材料に関する最近の研究成果発表会－材料研究に新しい風を－
  • Invited
• [Presentation] 「ケイ素を含む機能性有機結晶」 (2019)
  • Author(s): 山野井 慶徳
  • Organizer: 柏崎高校SSH高大連携プログラム
  • Invited
• [Presentation] ケイ素－ケイ素結合の特性を活用した外部刺激応答性分子の開発 (2018)
  • Author(s): 山野井 慶徳
  • Organizer: 新学術領域「ソフトクリスタル」 領域会議
• [Presentation] Synthesis and physical properties of tetrasila[2.2]thiophenophane derivatives for the luminescent and chiroptical materials (2017)
  • Author(s): Masaki Shimada，Yoshinori Yamanoi，Kenichiro Omoto，Shohei Tashiro，Mitsuhiko Shionoya，Tatsuhiko Ohto，Song-Toan Pham，Ryo Yamada，Hirokazu Tada，Mineyuki Hattori，Keiko Jimura，Shigenobu Hayashi，Hikaru Koike，Munetaka Iwamura，Koichi Nozaki， Hiroshi Nishihara
  • Organizer: 254th ACS National Meeting & Exposition
  • Int'l Joint Research
• [Presentation] 固体発光・円偏光発光を示すオクタメチルテトラシラ[2.2]シクロファンの創製 (2017)
  • Author(s): 島田真樹，山野井慶徳，小池ひかる，岩村宗高，野崎浩一，西原寛
  • Organizer: 第21回ケイ素化学シンポジウム
• [Presentation] The development of tetrasila[2.2]cyclophane derivatives for solid-state emission，electroluminescence，and circularly polarized luminescence (2017)
  • Author(s): 島田真樹，山野井慶徳，大戸達彦，山田亮，Pham Song-Toan，夛田博一，小池ひかる，岩村宗高，野崎浩一，西原寛
  • Organizer: 2017年光化学討論会
• [Remarks]
  • URL: http://www.chem.s.u-tokyo.ac.jp/users/inorg/index.html
• [Remarks]
  • URL: http://www.chem.s.u-tokyo.ac.jp/users/inorg/index.html
• [Remarks]
  • URL: https://www.softcrystal.org/
• [Remarks] 東京大学 大学院理学系研究科 化学専攻 無機化学研究室
  • URL: http://www.chem.s.u-tokyo.ac.jp/users/inorg/index.html
• [Remarks] 新学術領域研究「ソフトクリスタル」
  • URL: https://www.softcrystal.org/
• [Remarks] 東京大学大学院理学系研究科化学専攻無機化学研究室
  • URL: https://www.chem.s.u-tokyo.ac.jp/users/inorg/link.html