非平衡分子集合体の電子励起状態での光応答協同性発現機構の解明と電子準位制御

• Project Area: Application of Cooperative-Excitation into Innovative Molecular Systems with High-Order Photo-functions
• Project/Area Number: 15H01081
• 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: Shinshu University
• Principal Investigator: 伊藤 冬樹 信州大学, 学術研究院教育学系, 准教授 (80403921)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000); Fiscal Year 2016: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2015: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
• Keywords: 非平衡分子集合体 / 有機EL / 分子集合体 / 蛍光スペクトル / ジベンゾイルメタンフッ化ホウ素錯体 / 液滴クラスター

Outline of Annual Research Achievements

本研究では，有機分子集合化過程において発現する非平衡分子集合体の電子励起状態での光応答の協同性発現機構の解明とそれに基づく電子準位制御を目的とする．研究代表者は，有機結晶生成過程における蛍光スペクトルの劇的な変化と蛍光寿命の1桁以上の延伸，また集合体での波長選択的な高効率電子移動消光反応を見出した．そこで，協同的光応答に対する分子環境場・分子集合形態に依存した電子励起状態変調機構を解明し，その知見に基づいて多数励起分子によって集合体系でのみ形成される協同的作用に基づく電子準位制御を目標とした．
今年度は，ジベンゾイルメタンフッ化ホウ素錯体（BF2AVB）の非平衡分子集合状態の凍結と電子準位の決定を研究計画とし，実際の有機EL（OLED）への適用を行った．BF2AVBはその集合形態によって，紫色，青色，シアン色，緑色，橙色の発光を示すことがわかっている．これらの会合体形成と会合誘起エキシプレックス形成(AIEF)による全可視光域（青～緑～赤，＋白）にわたるOLEDの発光色制御を達成した．これは，色素会合体がエキシプレックスを形成すること，さらにそのエキシプレックスが熱活性遅延蛍光によって高効率かつ低ロールオフな発光を示すことに起因している．以上の知見に基づいて，単分子発光／会合発光／AIEFを制御することで青～緑～赤だけでなく白色発光OLEDも作成することが可能であることを実証した．
2年間の研究を通して，結晶生成過程の蛍光可視化および非平衡電子準位の制御を達成することができた．これらの知見は，所望の構造を有する結晶を選択的に生成できる結晶化条件の提供，結晶多形発現機構解明のための比較的容易な計測方法として利用されることが期待され，高度な集合体構造制御に重要な知見をもたらすものである．さらに，非平衡電子準位を利用したデバイス応用も実証できた．

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] リール第一大学/ENS Paris-saclay(フランス)
• [Int'l Joint Research] ENS Cachan/Lille Univeristy/Universite Paris 13(フランス)
• [Journal Article] AIE phenomena of a cyanostilbene derivative as a probe of molecular assembly process (2017)
  • Author(s): Fuyuki Ito, Jun-ichi Fujimori, Narumi Oka, Michel Sliwa, Cyril Ruckebusch, Syoji Ito and Hiroshi Miyasaka
  • Journal Title: Faraday Discussions Volume: 196 Pages: 231-243
  • DOI: 10.1039/c6fd00162a
  • NAID: 120007100075
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Concentration-dependent fluorescence color tuning of the difluoroboron avobenzone complex in polymer films (2017)
  • Author(s): Fuyuki Ito and Chika Kikuchi
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 90 Issue: 6 Pages: 709-713
  • DOI: 10.1246/bcsj.20170034
  • NAID: 130006770649
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Color Tuning of Avobenzone Boron Difluoride as an Emitter to Achieve Full-Color Emission (2016)
  • Author(s): Hin-Wai Mo, Youichi Tsuchiya, Yan Geng, Takehiro Sagawa, Chika Kikuchi, Hajime Nakanotani, Fuyuki Ito, and Chihaya Adachi
  • Journal Title: Adv. Funct. Mater. Volume: 26 Issue: 37 Pages: 6703-6710
  • DOI: 10.1002/adfm.201601257
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 蛍光分子を用いる有機結晶核形成段階の可視化とメカニズムの解明 (2016)
  • Author(s): 伊藤冬樹
  • Journal Title: 化学と工業 Volume: 69 Pages: 458-458
• [Journal Article] 結晶形成・成長の謎に蛍光で迫る (2016)
  • Author(s): 伊藤冬樹
  • Journal Title: 化学 Volume: 71 Pages: 70-71
• [Journal Article] Fluorescence Enhancement of a Dicyanostilbene Derivative Film Casted from an Alcoholic Solution Triggered by UV light Irradiation (2016)
  • Author(s): Jun-ichi Fujimori, Akio Katsuki, Fuyuki Ito
  • Journal Title: Chem. Lett. Volume: 45 Issue: 4 Pages: 421-423
  • DOI: 10.1246/cl.151195
  • NAID: 130005144004
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Substituent-Dependent Backward Reaction in Mechanofluorochromism of Dibenzoylmethanatoboron Difluoride Derivatives (2016)
  • Author(s): Takehiro Sagawa, Fuyuki Ito, Atsushi Sakai, Yudai Ogata, Keiji Tanaka, Hiroshi Ikeda
  • Journal Title: Photochem. Photobiol. Sci. Volume: 15 Issue: 3 Pages: 420-430
  • DOI: 10.1039/c5pp00453e
  • NAID: 120007100077
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Direct Visualization of the Two-step Nucleation Model by Fluorescence Color Changes during Evaporative Crystallization from Solution (2016)
  • Author(s): Fuyuki Ito, Yukino Suzuki, Jun-ichi Fujimori, Takehiro Sagawa, Mitsuo Hara, Takahiro Seki, Ryohei Yasukuni, and Marc Lamy de la Chapelle
  • Journal Title: Sci. Rep. Volume: 6 Issue: 1 Pages: 22918-22918
  • DOI: 10.1038/srep22918
  • NAID: 120007100076
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Properties and Evolution of Emission in Molecular Aggregates of a Perylene Ammonium Derivative in Polymer Matrices (2015)
  • Author(s): Fuyuki Ito, Hirofumi Sato, Yuri Ugachi, Narumi Oka, Syoji Ito and Hiroshi Miyasaka
  • Journal Title: Photochem. Photobiol. Sci. Volume: 14 Issue: 10 Pages: 1896-1902
  • DOI: 10.1039/c5pp00196j
  • NAID: 120007101498
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Solvent Viscosity Effect on Triplet-Triplet Pair in Triplet Fusion (2015)
  • Author(s): Kana Yokoyama, Yusuke Wakikawa, Tomoaki Miura, Jun-ichi Fujimori, Fuyuki Ito and Tadaaki Ikoma
  • Journal Title: The Journal of Physical Chemistry B Volume: 119 Issue: 52 Pages: 15901-15908
  • DOI: 10.1021/acs.jpcb.5b11208
  • Peer Reviewed
• [Presentation] Synergetic responses of the organic solids by the cooperative fluorescence modulation (2017)
  • Author(s): Fuyuki Ito
  • Organizer: Japan-France Workshop on photo-active nanomaterials with cooperative and synergetic responses
  • Place of Presentation: ENS Paris-Saclay, France
  • Year and Date: 2017-03-26
  • Int'l Joint Research / Invited
• [Presentation] Dynamics of Evaporative Crystallization Probed by Fluorescence Color Changes (2017)
  • Author(s): Fuyuki Ito
  • Organizer: 日本化学会第97春季年会，アジア国際シンポジウム-有機結晶ディビジョン-
  • Place of Presentation: 慶應義塾大学
  • Year and Date: 2017-03-16
  • Int'l Joint Research / Invited
• [Presentation] ジピロリルジケトンフッ化ホウ素錯体の溶媒蒸発結晶化過程における多形発現と相安定性 (2017)
  • Author(s): 岡 愛巳，伊藤冬樹，坂東勇哉，羽毛田洋平，山門陵平，前田大光，宮野哲也，藤内謙光，伊都将司，宮坂 博，尾関寿美男
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学
  • Year and Date: 2017-03-16
• [Presentation] ジベンゾイルメタンフッ化ホウ素錯体を導入したジフェニルアラニン誘導体の集合形態と蛍光特性 (2017)
  • Author(s): 狭川雄大，深港 豪，伊藤冬樹
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学
  • Year and Date: 2017-03-16
• [Presentation] Full-color emission tuning in OLED based on aggregation formation and aggregation induced exciplex formation (2017)
  • Author(s): Tsuchiya Youichi, Nakanotoni Hajime, Ito Fuyuki, Adachi Chihaya
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学
  • Year and Date: 2017-03-16
• [Presentation] 発光性ジケトン誘導体と層状ケイ酸塩との複合化 (2017)
  • Author(s): 廣瀬 睦，伊藤冬樹，岡田友彦
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学
  • Year and Date: 2017-03-16
• [Presentation] 蛍光変化で探る分子集合化過程のダイナミクス (2017)
  • Author(s): 伊藤冬樹
  • Organizer: 信州発！菌類・微生物×化学のコラボダイナミズム創発に向けて
  • Place of Presentation: 信州大学 長野（工学）キャンパス
  • Year and Date: 2017-03-08
  • Invited
• [Presentation] 蛍光スペクトルを用いたコロイド粒子・結晶生成過程の研究 (2016)
  • Author(s): 伊藤冬樹
  • Organizer: 信州コロイド&界面科学研究会第2回（2016年）研究討論会
  • Place of Presentation: 信州大学 長野（工学）キャンパス
  • Year and Date: 2016-10-28
  • Invited
• [Presentation] ジピロリルジケトンフッ化ホウ素錯体の蛍光変化に基づく多形発現過程の追跡 (2016)
  • Author(s): 岡 愛巳，伊藤冬樹，坂東勇哉，羽毛田洋平，山門陵平，前田大光，尾関寿美男
  • Organizer: 第25回有機結晶シンポジウム
  • Place of Presentation: 京都大学
  • Year and Date: 2016-09-18
• [Presentation] ジベンゾイルメタンフッ化ホウ素錯体の合成と粘土との複合化 (2016)
  • Author(s): 廣瀬 睦，伊藤冬樹，岡田友彦
  • Organizer: 第60回粘土科学討論会
  • Place of Presentation: 九州大学
  • Year and Date: 2016-09-15
• [Presentation] 蛍光変化に基づくジベンゾイルメタンフッ化ホウ素錯体の溶媒蒸発結晶化における分子集合ダイナミクス (2016)
  • Author(s): 伊藤冬樹，鈴木雪乃，藤森隼一，狭川雄大
  • Organizer: 第10回分子科学討論会
  • Place of Presentation: 神戸ファッションマート
  • Year and Date: 2016-09-13
• [Presentation] Photochemistry of molecular-assembly systems probed by the cooperative fluorescence modulation (2016)
  • Author(s): Fuyuki Ito
  • Organizer: 光化学討論会
  • Place of Presentation: 東京大学
  • Year and Date: 2016-09-06
• [Presentation] Direct Visualization of the Two-step Nucleation Model by Fluorescence Colour Changes during Evaporative Crystallization from Solution (2016)
  • Author(s): Fuyuki Ito
  • Organizer: 12th International Workshop of the Crystal Growth of Organic Materials (CGOM12)
  • Place of Presentation: Leeds University, UK
  • Year and Date: 2016-06-26
  • Int'l Joint Research / Invited
• [Presentation] 蛍光変化をプローブとした有機分子集合化過程の研究 (2016)
  • Author(s): 伊藤冬樹
  • Organizer: 超分子創製化学セミナー(第 66 回)
  • Place of Presentation: 立命館大学
  • Year and Date: 2016-05-20
  • Invited
• [Presentation] Crystal formation process observed by the fluorescence color changes (2016)
  • Author(s): Fuyuki Ito
  • Organizer: Toward an international laboratory between France & Japan on Photochemistry
  • Place of Presentation: French Embassy
  • Year and Date: 2016-04-01
  • Int'l Joint Research / Invited
• [Presentation] Photochemistry of Molecular-assembly Systems Probed by the Fluorescence Modulation (2016)
  • Author(s): Fuyuki Ito
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学
  • Year and Date: 2016-03-26
  • Int'l Joint Research / Invited
• [Presentation] ルミネッセンス化学研究を通した教員養成・アウトリーチ活動 (2016)
  • Author(s): 伊藤冬樹
  • Organizer: 日本化学会第96春季年会 特別企画「ルミネッセンス化学アンサンブル」
  • Place of Presentation: 同志社大学
  • Year and Date: 2016-03-24
  • Invited
• [Presentation] Fluorescence Visualization of Solvent Evaporative Crystallization (2016)
  • Author(s): Fuyuki Ito
  • Organizer: Seminar Invite Laboratoire CSPBAT
  • Place of Presentation: Universite Paris 13
  • Year and Date: 2016-02-22
  • Invited
• [Presentation] Cooperative fluorescence color changes of a dibenzoylmethane boron complex during the molecular assembling process (2015)
  • Author(s): Fuyuki Ito, Yukino Suzuki, Jun-ichi Fujimori and Takehiro Sagawa
  • Organizer: International Chemical Congress of Pacific Basin Societies (PacifiChem 2015)
  • Place of Presentation: Hawaii
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Fluorescence Visualization of Molecular Assembly Processes during Solvent Evaporation (2015)
  • Author(s): Fuyuki Ito
  • Organizer: 國立交通大學應用化學系 104年 前瞻跨領域基礎科學中心 尖端生物分子探測 専題演講
  • Place of Presentation: 台湾国立交通大学
  • Year and Date: 2015-11-17
  • Invited
• [Presentation] 会合誘起増強発光性分子の分子集合化にともなう動的および静的蛍光変化 (2015)
  • Author(s): 伊藤冬樹，藤森隼一，岡 愛巳，伊都将司，宮坂 博
  • Organizer: 第24回有機結晶シンポジウム
  • Place of Presentation: 広島大学
  • Year and Date: 2015-11-01
• [Presentation] 蛍光変化に基づくジベンゾイルメタンフッ化ホウ素錯体の結晶生成ダイナミクス (2015)
  • Author(s): 伊藤冬樹，鈴木雪乃，藤森隼一，狭川雄大
  • Organizer: 2015年光化学討論会
  • Place of Presentation: 大阪市立大学
  • Year and Date: 2015-09-11
• [Presentation] 非平衡分子集合体の電子励起状態での光応答協同性発現機構の解明 (2015)
  • Author(s): 伊藤冬樹
  • Organizer: アルプスサイエンスセミナー
  • Place of Presentation: 乗鞍ステーション（長野県松本市）
  • Year and Date: 2015-08-28
  • Invited
• [Presentation] Molecular dynamics of initial stage of crystal formation process as detected by aggregation-induced emission (2015)
  • Author(s): Fuyuki Ito, Jun-ichi Fujimori, Shoji Ito and Hiroshi Miyasaka
  • Organizer: 22nd International Conference on the Chemistry of the Organic Solid State (ICCOSS 2015)
  • Place of Presentation: Niigata, Japan
  • Year and Date: 2015-07-17
  • Int'l Joint Research
• [Presentation] Fluorescence properties of Dibenzoylmethane Boron complex depending on the aggregated states in polymer films and crystallization process (2015)
  • Author(s): Fuyuki Ito, Yukino Suzuki, Jun-ichi Fujimori and Takehiro Sagawa
  • Organizer: 27th International Conference on Photochemistry (ICP 2015)
  • Place of Presentation: Jeju, Korea
  • Year and Date: 2015-07-02
  • Int'l Joint Research
• [Remarks] 研究室ホームページ
  • URL: http://www.shinshu-u.ac.jp/faculty/education/course/science/chemistry2/index.html