不斉結晶のメカノクロミズム：汎用的刺激応答性材料の設計と新機能の開拓

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 17H05344
• 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: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2018: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2017: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 配位 / 錯体 / キラル / 相転移 / 結晶 / 発光 / 不斉 / メカノクロミズム / 包接 / 発光性メカノクロミズム / アシンメトリー / キラリティ / 金錯体 / 単結晶

Outline of Annual Research Achievements

我々は、アリール金イソシアニド錯体からなる発光性メカノクロミック分子の研究に取り組んできた。メカノクロミズムとは、固体の発光の色が磨砕や力学適応力により切り替わる現象である。固体をこするというシンプルな外部刺激によって分子の機能（発光）が切り替わる点が興味深く、センサーやディスプレイとして応用が可能とされている。本研究では、発光性メカノクロミズムを示す金錯体に対してキラリティの要素を組み込むことで、新奇刺激応答性材料の開発を試みる。
あるアキラルな金錯体が、機械的刺激を与えることでその発光特性が変化するメカノクロミズムを示すことを見出した。この錯体の機械的刺激を印加する前の結晶構造を調べると、水素結合を介して集合した結晶構造を構築していた。粉末エックス線回折測定により、機械的刺激を印加した後の分子配列を調査したところアモルファスであることがわかり、結晶－アモルファス相転移によって発光変化が起こったことが明らかとなった。水素結合を形成した結晶構造にヒントを得て、この金錯体と水素結合が可能なゲスト分子との共結晶化を行うと、意図したとおり、金錯体とゲスト分子からなる共結晶を形成した。その同定は、X線構造解析とNMR、元素分析により行った。この共結晶は、金錯体のみで結晶化した場合とは発光特性やメカノクロミズム特性が異なることがわかった。今後は、キラリティを持つゲスト分子との複合化を行い、その発光性クロミック特性を評価する。

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