発光性ベンディングクロミック結晶の開発と応用

• Project Area: pi-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions
• Project/Area Number: 17H05134
• 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: Hokkaido University
• Principal Investigator: 関 朋宏 北海道大学, 工学研究院, 助教 (50638187)
• Project Period (FY): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000); Fiscal Year 2018: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2017: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
• Keywords: メカノクロミズム / 金錯体 / 結晶 / 相転移 / 発光 / 屈曲 / 塑性・弾性 / 発光性メカノクロミズム / 弾性変形 / 塑性変形 / 有機結晶 / 単結晶 / 結晶屈曲

Outline of Annual Research Achievements

金属錯体や有機分子の結晶（有機結晶）は、従来硬くて脆く機械的な強度が非常に弱い。一方、機械的に力をくわえても、壊れずに折れ曲がる有機結晶が近年盛んに研究されている。屈曲する有機結晶の利点は、X線を用いた単結晶構造解析により、結晶を構成する分子配列を高精度に調査できる点であり、屈曲挙動の分子レベルの理解に有用である。我々はこれまで金錯体の発光性メカノクロミズムを精力的に研究してきた。一般に発光性メカノクロミズムとは、機械的刺激により固体材料の発光特性が変化する現象のことである。本研究では、屈曲がきっかけとなり発光が変化する結晶、すなわち「ベンディングクロミック結晶」の開発を目的とする。

我々は、ある金錯体に対してハロゲンユニットを導入しところ、その錯体からなる結晶が、応力を印加することで、結晶が壊れることなく顕著な屈曲特性を示すことをみいだした。導入するハロゲン部位の数や置換位置を変化させることで、発光色が青から黄色に変化することも見出した。類似する屈曲性分子結晶と比較しても、このようにバラエティにとんだ発光特性を示す例は少ない。X線を用いた構造解析の結果、いずれの金錯体の結晶構造においても、ハロゲン間の相互作用が顕著に見られ、このことが、結晶が壊れずに屈曲可能となることを可能にしていると考えられる。現在発光色の多様化とクロミック挙動に関して調査を行っており、得られた成果を論文にまとめている段階である。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide Complexes: Theoretical Study with QM/MM Approach (2019)
  • Author(s): Aono Shinji、Seki Tomohiro、Ito Hajime、Sakaki Shigeyoshi
  • Journal Title: The Journal of Physical Chemistry C Volume: 123 Issue: 8 Pages: 4773-4794
  • DOI: 10.1021/acs.jpcc.8b10602
  • Peer Reviewed
• [Journal Article] Luminescent mechanochromism of gold N-heterocyclic carbene complexes with hypso- and bathochromic spectral shifts (2019)
  • Author(s): Seki Tomohiro、Kashiyama Kentaro、Ito Hajime
  • Journal Title: Dalton Transactions Volume: 印刷中 Issue: 21 Pages: 7105-7109
  • DOI: 10.1039/c9dt00566h
  • NAID: 120006849864
  • Peer Reviewed
• [Journal Article] Anisotropic strain release in a thermosalient crystal: correlation between the microscopic orientation of molecular rearrangements and the macroscopic mechanical motion (2019)
  • Author(s): Seki Tomohiro、Mashimo Takaki、Ito Hajime
  • Journal Title: Chemical Science Volume: 印刷中 Issue: 15 Pages: 4185-4191
  • DOI: 10.1039/c8sc05563g
  • Peer Reviewed
• [Journal Article] A meta-diisocyanide benzene-based aryl gold isocyanide complex exhibiting multiple solid-state molecular arrangements and luminescent mechanochromism (2018)
  • Author(s): Seki Tomohiro、Ida Kentaro、Ito Hajime
  • Journal Title: Materials Chemistry Frontiers Volume: 2 Issue: 6 Pages: 1195-1200
  • DOI: 10.1039/c8qm00074c
  • NAID: 120006636178
  • Peer Reviewed / Open Access
• [Journal Article] Spin-orbit coupling dependent energy transfer in luminescent nonanuclear Yb-Gd / Yb-Lu clusters (2018)
  • Author(s): Omagari Shun、Nakanishi Takayuki、Kitagawa Yuichi、Seki Tomohiro、Fushimi Koji、Ito Hajime、Meijerink Andries、Hasegawa Yasuchika
  • Journal Title: Journal of Luminescence Volume: 201 Pages: 170-175
  • DOI: 10.1016/j.jlumin.2018.04.049
  • NAID: 120006882064
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Light-regulated crystal growth of π-conjugated luminophores in an azobenzene matrix (2018)
  • Author(s): Kobayashi Takuji、Kitamoto Yuichi、Hirai Yu、Kajitani Takashi、Seki Tomohiro、Yagai Shiki
  • Journal Title: Communications Chemistry Volume: 1 Issue: 1 Pages: 58-58
  • DOI: 10.1038/s42004-018-0061-8
  • Peer Reviewed / Open Access
• [Journal Article] Spiral Eu(III) coordination polymers with circularly polarized luminescence (2018)
  • Author(s): Yasuchika Hasegawa, Yui Miura, Yuichi Kitagawa, Satoshi Wada, Takayuki Nakanishi, Koji Fushimi, Tomohiro Seki, Hajime Ito, Takeshi Iwasa, Tetsuya Taketsugu, Masayuki Gon, Kazuo Tanaka, Yoshiki Chujo, Shingo Hattori, Masanobu Karasawa and Kazuyuki Ishii
  • Journal Title: Chemical Communications Volume: 54 Issue: 76 Pages: 10695-10697
  • DOI: 10.1039/c8cc05147j
  • NAID: 120006727594
  • Peer Reviewed
• [Journal Article] A gold isocyanide complex with a pendant carboxy group: orthogonal molecular arrangements and hypsochromically shifted luminescent mechanochromism (2018)
  • Author(s): Seki Tomohiro、Kobayashi Koh、Mashimo Takaki、Ito Hajime
  • Journal Title: Chemical Communications Volume: 54 Issue: 79 Pages: 11136-11139
  • DOI: 10.1039/c8cc06490c
  • NAID: 120006729573
  • Peer Reviewed
• [Journal Article] Synthesis and Evaluation of 1,3a,6a-triazapentalene (TAP)-bonded system (2018)
  • Author(s): M. Ito, A. Mera, T. Mashita, T. Seki, J. Nakayama, E. Ohashi, K. Sangit, T. Hamura, H. Ito, K. Nanba
  • Journal Title: Chem. Eur. J. Volume: 24 Issue: 67 Pages: 17727-17730
  • DOI: 10.1002/chem.201804733
  • NAID: 120006768206
  • Peer Reviewed
• [Journal Article] Structural Manipulation of Triboluminescent Lanthanide Coordination Polymers by Side-Group Alteration (2018)
  • Author(s): Hirai Yuichi、Ferreira da Rosa Pedro Paulo、Nakanishi Takayuki、Kitagawa Yuichi、Fushimi Koji、Seki Tomohiro、Ito Hajime、Hasegawa Yasuchika
  • Journal Title: Inorganic Chemistry Volume: 57 Issue: 23 Pages: 14653-14659
  • DOI: 10.1021/acs.inorgchem.8b02367
  • Peer Reviewed
• [Journal Article] Soft Crystal Force Field for Reproducing the Crystal Structures of Aryl Gold Isocyanide Complexes (2018)
  • Author(s): NAKAYAMA Naofumi、OBATA Shigeaki、HORI Yoshikazu、GOTO Hitoshi、SEKI Tomohiro、ITO Hajime
  • Journal Title: Journal of Computer Chemistry, Japan Volume: 17 Issue: 3 Pages: 155-157
  • DOI: 10.2477/jccj.2018-0031
  • NAID: 130007503976
  • ISSN: 1347-1767, 1347-3824
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and Photophysical Properties of Eu(III) Complexes with Phosphine Oxide Ligands Including Metal Ions (2018)
  • Author(s): M. Yamamoto, T. Nakanishi, Y. Kitagawa, T. Seki, H. Ito, K. Fushimi, Y. Hasegawa
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 91 Issue: 1 Pages: 6-11
  • DOI: 10.1246/bcsj.20170241
  • NAID: 130006309063
  • Peer Reviewed
• [Journal Article] A Luminescent Dinuclear EuIII/TbIII Complex with LMCT Band as a Single-Molecular Thermosensor (2018)
  • Author(s): Yanagisawa Kei、Kitagawa Yuichi、Nakanishi Takayuki、Seki Tomohiro、Fushimi Koji、Ito Hajime、Hasegawa Yasuchika
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 8 Pages: 1956-1961
  • DOI: 10.1002/chem.201705021
  • NAID: 120006552868
  • Peer Reviewed
• [Journal Article] Mechanical-Stimulation-Triggered and Solvent-Vapor-Induced Reverse Single-Crystal-to-Single-Crystal Phase Transitions with Alterations of the Luminescence Color (2018)
  • Author(s): Jin Mingoo、Sumitani Toshiki、Sato Hiroyasu、Seki Tomohiro、Ito Hajime
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 8 Pages: 2875-2879
  • DOI: 10.1021/jacs.7b12455
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Triboluminescence of Lanthanide Coordination Polymers with Face-to-Face Arranged Substituents (2017)
  • Author(s): Hirai Yuichi、Nakanishi Takayuki、Kitagawa Yuichi、Fushimi Koji、Seki Tomohiro、Ito Hajime、Hasegawa Yasuchika
  • Journal Title: Angewandte Chemie International Edition Volume: 56 Issue: 25 Pages: 7171-7175
  • DOI: 10.1002/anie.201703638
  • NAID: 120006473599
  • Peer Reviewed
• [Journal Article] Luminescent Mechanochromic 9-Anthryl Gold(I) Isocyanide Complex with an Emission Maximum at 900 nm after Mechanical Stimulation (2017)
  • Author(s): Seki Tomohiro、Tokodai Noriaki、Omagari Shun、Nakanishi Takayuki、Hasegawa Yasuchika、Iwasa Takeshi、Taketsugu Tetsuya、Ito Hajime
  • Journal Title: Journal of The American Chemical Society Volume: 139 Issue: 19 Pages: 6514-6517
  • DOI: 10.1021/jacs.7b00587
  • Peer Reviewed
• [Journal Article] Low-temperature-selective luminescent mechanochromism of a thienyl gold isocyanide complex (2017)
  • Author(s): Seki Tomohiro、Kobayashi Koh、Ito Hajime
  • Journal Title: Chemical Communications Volume: 53 Issue: 50 Pages: 6700-6703
  • DOI: 10.1039/c7cc03190d
  • NAID: 120006482567
  • Peer Reviewed
• [Journal Article] Mechano-Responsive Luminescence via Crystal-to-Crystal Phase Transitions between Chiral and Non-Chiral Space Groups (2017)
  • Author(s): Jin Mingoo、Seki Tomohiro、Ito Hajime
  • Journal Title: Journal of the American Chemical Society Volume: 139 Issue: 22 Pages: 7452-7455
  • DOI: 10.1021/jacs.7b04073
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Tuning the Lifetime of Transient Phases of Mechanochromic Gold Isocyanide Complexes through Functionalization of the Terminal Moieties of Flexible Side Chains (2017)
  • Author(s): Tomohiro Seki, Kentaro Kashiyama, Shiki Yagai, Hajime Ito
  • Journal Title: Chemistry Letters Volume: 46 Issue: 9 Pages: 1415-1418
  • DOI: 10.1246/cl.170482
  • NAID: 130006067887
  • Peer Reviewed / Open Access
• [Journal Article] Enhanced Luminescence of Asymmetrical Seven-Coordinate EuIII Complexes Including LMCT Perturbation (2017)
  • Author(s): Yanagisawa Kei、Kitagawa Yuichi、Nakanishi Takayuki、Akama Tomoko、Kobayashi Masato、Seki Tomohiro、Fushimi Koji、Ito Hajime、Taketsugu Tetsuya、Hasegawa Yasuchika
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2017 Issue: 32 Pages: 3843-3848
  • DOI: 10.1002/ejic.201700815
  • NAID: 120006502496
  • Peer Reviewed
• [Journal Article] Tris(trimethylsilyl)silylboronate Esters: Novel Bulky, Air- and Moisture-Stable Silylboronate Ester Reagents for Boryl Substitution and Silaboration Reactions (2017)
  • Author(s): Yamamoto Eiji、Shishido Ryosuke、Seki Tomohiro、Ito Hajime
  • Journal Title: Organometallics Volume: 36 Issue: 16 Pages: 3019-3022
  • DOI: 10.1021/acs.organomet.7b00476
  • Peer Reviewed
• [Journal Article] Phosphorescence Control Mediated by Molecular Rotation and Aurophilic Interactions in Amphidynamic Crystals of 1,4-Bis[tri-(p-fluorophenyl)phosphane-gold(I)-ethynyl]benzene (2017)
  • Author(s): Jin Mingoo、Chung Tim S.、Seki Tomohiro、Ito Hajime、Garcia-Garibay Miguel A.
  • Journal Title: Journal of the American Chemical Society Volume: 139 Issue: 49 Pages: 18115-18121
  • DOI: 10.1021/jacs.7b11316
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Origin of Concentration Quenching in Ytterbium Coordination Polymers: Phonon-Assisted Energy Transfer (2017)
  • Author(s): Omagari Shun、Nakanishi Takayuki、Hirai Yuichi、Kitagawa Yuichi、Seki Tomohiro、Fushimi Koji、Ito Hajime、Hasegawa Yasuchika
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2018 Issue: 5 Pages: 561-567
  • DOI: 10.1002/ejic.201701040
  • Peer Reviewed
• [Presentation] アルケニル金イソシアニド錯体のサーモサリエント効果とそのメカニズム調査 (2019)
  • Author(s): 関 朋宏 眞下 峻希 伊藤 肇
  • Organizer: 日本化学会第99春季年会(1D7-30)
• [Presentation] Luminescent Mechanochromic Gold Complex Exhibiting Phase Transition between Crystalline Phases (2018)
  • Author(s): Tomohiro Seki
  • Organizer: 233rd ECS Meeting
  • Int'l Joint Research / Invited
• [Presentation] Reversible Single-Crystal-to-Single-Crystal Phase Transformations with Emission Color Changes Initiated by Mechanical Stimulation and Solvent Vapor (2018)
  • Author(s): Tomohiro Seki, Jin Mingoo, Toshiki Sumitani, Hajime Ito
  • Organizer: the 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] 芳香族金イソシアニド錯体の外部刺激応答特性 (2018)
  • Author(s): 関 朋宏
  • Organizer: 2018年度北海道高分子若手研究会
  • Invited
• [Presentation] Gold Complexes Exhibiting Luminescent Mechanochomism (2018)
  • Author(s): Tomohiro Seki
  • Organizer: 3rd International Caparica Conference on Chromogenic and Emissive Materials (IC3EM 2018)
  • Int'l Joint Research / Invited
• [Presentation] 発光色変化や機械的応答を示す外部刺激応答性金錯体 (2018)
  • Author(s): 関 朋宏
  • Organizer: 若手研究者のための有機合成化学札幌セミナー
  • Invited
• [Presentation] Reversible phase transition between single crystals of luminescent gold complex (2018)
  • Author(s): Tomohiro Seki
  • Organizer: 15th International Conference of the Asian Crystallographic Association (AsCA 2018)
  • Int'l Joint Research / Invited
• [Presentation] Infrared-Emissive Luminescent Mechanochromism of Anthryl Gold Isocyanide Complex (2018)
  • Author(s): Tomohiro Seki
  • Organizer: International Congress on Pure & Applied Chemistry (ICPAC) 2018
  • Int'l Joint Research / Invited
• [Presentation] 機械的刺激と溶媒蒸気により誘起される発光性金錯体の可逆的単結晶－単結晶相転移 (2018)
  • Author(s): 関 朋宏 墨谷 俊輝 陳 旻究 伊藤 肇
  • Organizer: 日本化学会第98春季年会
• [Presentation] 発光性メカノクロミズムと各種刺激応答性を示す金錯体の研究 (2017)
  • Author(s): 関 朋宏
  • Organizer: 第58回π造形コロキウム
  • Invited
• [Presentation] Luminescent Mechanochromism of Gold Isocyanide Exhibiting Various Emission Colors (2017)
  • Author(s): Tomohiro Seki
  • Organizer: π-Figuration German-Japanese Workshop Heidelberg
  • Int'l Joint Research