Preparation and photo-functional properties of lanthanide coordination nanoparticles

• Project/Area Number: 18H02041
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 35030:Organic functional materials-related
• Research Institution: Hokkaido University
• Principal Investigator: HASEGAWA Yasuchika 北海道大学, 工学研究院, 教授 (80324797)
• Co-Investigator(Kenkyū-buntansha): 伏見 公志 北海道大学, 工学研究院, 准教授 (20271645) ; 中西 貴之 国立研究開発法人物質・材料研究機構, 機能性材料研究拠点, 主任研究員 (30609855) ; 北川 裕一 北海道大学, 化学反応創成研究拠点, 特任講師 (90740093)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000); Fiscal Year 2020: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2019: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000); Fiscal Year 2018: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
• Keywords: ナノ粒子 / 配位高分子 / 発光 / 希土類 / 希土類錯体 / 表面修飾

Outline of Final Research Achievements

In this study, preparations and three-dimensional structural control of luminescent lanthanide coordination nanoparticles have been demonstrated for creation of new molecular materials. Mono-nuclear lanthanide complexes were attached using surface-modified linker ligands on the nanoparticles. Eu(III) complexes fixed on the CaS and SiO2 nanoparrticles show bright red-luminescence. Lanthanide coordination polymers were also fixed on the nanoparticles. The three-dimensional structural control of luminescent lanthanide coordination polymers successfully promoted increase of their emission quantum yields.

Academic Significance and Societal Importance of the Research Achievements

この希土類錯体は色純度の高い発光を示すことから、ディスプレイや発光プラスチックに関する研究が多く報告されている。さらに、その発光寿命は数百マイクロ秒であることから生体マーカーなどの研究例も多い。セキュリティー関連分野や太陽電池および温度センシングできる希土類配位高分子の研究が活発に行われている。
本研究ではナノ粒子の表面に希土類錯体および配位高分子の固定化と強発光化を実現した。さらに、希土類配位高分子のナノ立体構造制御と強発光化に関する重要な学術知見を得ることができた。ナノサイズ化された希土類配位高分子は実用的なハイブリッド機能材料として今後重要になると考えられる。

Research Products

• [Journal Article] First Tribo‐Excited Chemical Reaction of a Stacked Lanthanide Coordination Polymer with an in Situ Reaction Monitor (2021)
  • Author(s): Kitagawa Yuichi、Naito Ayu、Fushimi Koji、Hasegawa Yasuchika
  • Journal Title: Chemistry A European Journal Volume: 27 Issue: 7 Pages: 2279-2283
  • DOI: 10.1002/chem.202004485
  • Peer Reviewed
• [Journal Article] Thermo‐Sensitive Eu III Coordination Polymers with Amorphous Networks (2021)
  • Author(s): Hasegawa Yasuchika、Sato Natsumi、Hayashi Joe、Kitagawa Yuichi、Fushimi Koji
  • Journal Title: ChemistrySelect Volume: 6 Issue: 12 Pages: 2812-2816
  • DOI: 10.1002/slct.202100531
  • Peer Reviewed
• [Journal Article] Long‐Range LMCT Coupling in EuIII Coordination Polymers for an Effective Molecular Luminescent Thermometer** (2020)
  • Author(s): Kitagawa Yuichi、Kumagai Marina、Ferreira da Rosa Pedro Paulo、Fushimi Koji、Hasegawa Yasuchika
  • Journal Title: Chemistry A European Journal Volume: 27 Issue: 1 Pages: 264-269
  • DOI: 10.1002/chem.202002628
  • Peer Reviewed
• [Journal Article] An Europium(III) Luminophore with Pressure‐Sensing Units: Effective Back Energy Transfer in Coordination Polymers with Hexadentate Porous Stable Networks (2020)
  • Author(s): Hasegawa Yasuchika、Sawanobori Takuya、Kitagawa Yuichi、Shoji Sunao、Fushimi Koji、Nakasaka Yuta、Masuda Takao、Hisaki Ichiro
  • Journal Title: ChemPlusChem Volume: 85 Issue: 9 Pages: 1989-1993
  • DOI: 10.1002/cplu.202000513
  • NAID: 120007145355
  • Peer Reviewed
• [Journal Article] Luminescent lanthanide complex with seven-coordination geometry (2020)
  • Author(s): P.-P. Ferreira da Rosa, Y. Kitagawa, Y. Hasegawa
  • Journal Title: Coordination Chemistry Reviews Volume: 406 Pages: 213153-213153
  • DOI: 10.1016/j.ccr.2019.213153
  • Peer Reviewed
• [Journal Article] First aggregation-induced emission of a Tb(III) luminophore based on modulation of ligand; ligand charge transfer bands (2020)
  • Author(s): Y. Kitagawa, M. Kumagai, T. Nakanishi, K. Fushimia and Y. Hasegawa
  • Journal Title: Dalton Trans. Volume: 49 Issue: 10 Pages: 2431-2436
  • DOI: 10.1039/d0dt00528b
  • Peer Reviewed
• [Journal Article] Near-IR luminescent Yb(III) coordination polymers composed of pyrene derivatives for thermo-stable oxygen sensors (2019)
  • Author(s): Y. Hasegawa, T. Matsui, Y. Kitagawa, T. Nakanishi, T. Seki, H. Ito, Y. Nakasaka, T. Masuda, K. Fushimi
  • Journal Title: Chem. Eur. J. Volume: 25 Issue: 53 Pages: 12308-12315
  • DOI: 10.1002/chem.201902583
  • Peer Reviewed
• [Journal Article] Lifetimes of Lanthanide(III) Triboluminescence Excited by Aerodynamic Shock Waves (2019)
  • Author(s): Hirai Yuichi、Kotani Akira、Sakaue Hirotaka、Kitagawa Yuichi、Hasegawa Yasuchika
  • Journal Title: The Journal of Physical Chemistry C Volume: 123 Issue: 44 Pages: 27251-27256
  • DOI: 10.1021/acs.jpcc.9b08349
  • Peer Reviewed / Int'l Joint Research
• [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] Ligand-Assisted Back Energy Transfer in Luminescent TbIII Complexes for Thermosensing Properties (2018)
  • Author(s): Yamamoto Masanori、Kitagawa Yuichi、Nakanishi Takayuki、Fushimi Koji、Hasegawa Yasuchika
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 67 Pages: 17719-17726
  • DOI: 10.1002/chem.201804392
  • NAID: 120006769954
  • Peer Reviewed
• [Journal Article] Electronic chirality inversion of lanthanide complex induced by achiral molecules (2018)
  • Author(s): Wada Satoshi、Kitagawa Yuichi、Nakanishi Takayuki、Gon Masayuki、Tanaka Kazuo、Fushimi Koji、Chujo Yoshiki、Hasegawa Yasuchika
  • Journal Title: Scientific Reports Volume: 8 Issue: 1 Pages: 16395-16395
  • DOI: 10.1038/s41598-018-34790-0
  • NAID: 120006543299
  • Peer Reviewed / Open Access
• [Presentation] フェナントレン骨格を導入した二核希土類錯体の長寿命発光特性 (2021)
  • Author(s): 島かおり，北川裕一，伏見公志，長谷川靖哉
  • Organizer: 化学系学協会北海道支部2021年冬季研究発表会(オンライン)
• [Presentation] ポリエーテル鎖を有するEu(III)錯体の光物性 (2021)
  • Author(s): 河野允哉，庄司淳，北川裕一，伏見公志，長谷川靖哉
  • Organizer: 化学系学協会北海道支部2021年冬季研究発表会(オンライン)
• [Presentation] Circularly polarized luminescence of chiral Eu(III) lanthanide coordination polymer with phase transition behaiviors (2020)
  • Author(s): M. Tsurui, Y. Kitagawa, K. Fushimi, M. Gon, K. Tanaka, Y. Hasegawa
  • Organizer: 2020年web光化学討論会
• [Presentation] Luminescence properties of lanthanide complexes with tetraethyleneglycol group (2020)
  • Author(s): M. Kono, S. Shoji, Y. Kitagawa, K. Fushimi, Y. Hasegawa
  • Organizer: 2020年web光化学討論会
• [Presentation] Control of LMCT state in seven- and eight-coordinated Eu(III) complexes (2020)
  • Author(s): P.-P. Ferreira da ROSA, S. Miyazaki, Y. Kitagawa, K. Miyata, T. Akama, M. Kobayashi, K. Fushimi, K. Onda, T. Taketsugu, Y. Hasegawa
  • Organizer: 2020年web光化学討論会
• [Presentation] Eu(III)-functionalized Hybrid Nanomaterials With Enhanced Luminescence Properties (2020)
  • Author(s): T. Zhang, MD J. Islam, Y. Kitagawa, Y. Hasegawa
  • Organizer: 錯体化学会第70回討論会(オンライン)
• [Presentation] Mechanochemical oxidation of Eu(III) coordination polymer containing anthracene frameworks (2020)
  • Author(s): A. NAITO, Y. KITAGAWA, K. FUSHIMI, Y. HASEGAWA
  • Organizer: 錯体化学会第70回討論会(オンライン)
• [Presentation] フェナントレン骨格を導入した二核希土類錯体の発光特性 (2020)
  • Author(s): 島かおり, 北川裕一, 熊谷まりな, 伏見公志, 長谷川靖哉
  • Organizer: 錯体化学会第70回討論会(オンライン)
• [Presentation] Photophysical properties of Eu(III) coordination polymer including amide groups (2020)
  • Author(s): J. Hayashi, S. Shoji, Y. Kitagawa, K. Fushimi, Y. Hasegawa
  • Organizer: 3rd G'L'owing Polymer Symposium in KANTO(Web)
• [Presentation] 希土類配位高分子が拓く次世代光機能材料の創成 (2020)
  • Author(s): 長谷川靖哉
  • Organizer: 第29回ポリマー材料フォーラム, 高分子学会(Web)
  • Invited
• [Presentation] 強発光する希土類配位高分子の設計と応用展開 (2020)
  • Author(s): 長谷川靖哉
  • Organizer: 光化学応用講座2020,オンライン
  • Invited
• [Presentation] カルボラン骨格を導入した希土類配位高分子の合成と物性評価 (2019)
  • Author(s): 齋藤康樹, 北川裕一, 伏見公志, 長谷川靖哉
  • Organizer: 第３５回希土類討論会
• [Presentation] Eu(III) and Tb(III) Coordination polymers with strong luminerscence and photo-functional properties (2019)
  • Author(s): Y. Hasegawa
  • Organizer: International Conference on Photocatalysis and Photoenergy 2019 (ICoPP2019)
  • Int'l Joint Research / Invited
• [Presentation] Tb配位高分子における連結配位子構造変化と発光機能評価 (2019)
  • Author(s): 森明竜馬, 北川裕一, 伏見公志,長谷川靖哉
  • Organizer: 日本化学会北海道支部会2019年夏季研究発表会
• [Presentation] 発光性希土類配位高分子における連結配位子の置換基効果 (2019)
  • Author(s): 森明竜馬, 北川裕一, 伏見公志,長谷川靖哉
  • Organizer: 第３１回配位化合物の光化学討論会
• [Presentation] Synehesesand photophysical properties of Eu(III) coordination polymers built with triphenylene backbones (2019)
  • Author(s): T. Sawanobori, Y.Kitagawa, S.Shoji,I.Hisaki, K.Fushimi, Y.Hasegawa
  • Organizer: 2019年光化学討論会
• [Presentation] Bright luminescence of Eu(III) complex containing chrysene framework for thermosensitive paints (2019)
  • Author(s): M.Kumagai, Y.Kitagawa, K.Fushimi, Y.Hasegawa
  • Organizer: 錯体化学会第69回討論会
• [Presentation] CaSナノ粒子に固定化されたEu(III)錯体の発光特性 (2018)
  • Author(s): 沢登拓矢, 北川裕一, 中西貴之, 伏見公志, 長谷川靖哉
  • Organizer: 第３０回配位化合物の光化学討論会
• [Presentation] Immobilization of Eu(III) complexes inCaS nanoparticles (2018)
  • Author(s): T.Sawanobori, Y. Kitagawa, T.Nakanishi, K. Fushimi, Y.Hasegawa
  • Organizer: 錯体化学会第６８回討論会
• [Presentation] 発光性Eu(III)錯体を固定化したCaSナノ粒子の合成 (2018)
  • Author(s): 沢登拓矢, 北川裕一, 中西貴之, 伏見公志, 長谷川靖哉
  • Organizer: 第８回CSJ化学フェスタ
• [Patent(Industrial Property Rights)] 発光材料、発光インク、発光体及び発光デバイス (2020)
  • Inventor(s): 長谷川靖哉, ツァンテン, 北川裕一
  • Industrial Property Rights Holder: 北海道大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2020-119391
  • Filing Date: 2020
• [Patent(Industrial Property Rights)] 希土類錯体、発光体及び発光デバイス (2018)
  • Inventor(s): 長谷川靖哉, 北川裕一, 他
  • Industrial Property Rights Holder: 長谷川靖哉, 北川裕一, 他
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2018-158240
  • Filing Date: 2018