非対称配位圏がもたらす金属錯体の光新機能

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 17H05354
• 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: Kyoto University (2018); The University of Tokyo (2017)
• Principal Investigator: 坂本 良太 京都大学, 工学研究科, 准教授 (80453843)
• Project Period (FY): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000); Fiscal Year 2018: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000); Fiscal Year 2017: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 非対称性 / アシンメトリー / ジピリン / 金属錯体 / ナノワイヤ / 非対称配位圏 / テルピリジン / 円偏光発光 / 非対称 / キラリティ / 発光

Outline of Annual Research Achievements

一次元ポリマーの単一分子鎖は金属・半導体ナノ材料よりも微小な究極のナノ材料となりうる. 加えて, ランダム・ブロック・交互共重合など様々なヘテロ構造の構築法が確立されており, そのバリエーションも潤沢である. しかしながら, 単一ポリマー鎖1本の取扱・分析・機能いずれも発展途上の状況にあり, ナノ材料としての利用は極めて限定的である. この状況を打破するべく, 筆者が開発したジピリンナノワイヤ (JACS 2017; Chem. Sci. 2015) は有機溶媒中で超音波処理し, その分散液をHOPG 基板にキャストすることで3 μmを超える長大単一ワイヤが観測される. そこで本研究では, 単一ポリマー鎖に剥離可能なジピリンナノワイヤの共重合体を合成し, 分子性単一ナノワイヤのヘテロ構造を通常環境下で可視化する手法・条件の確立を目指した. 今年度は単重合体と共重合体とを大気化AFMの高さ情報として識別できることを見出した (Science Adv. 2019). 本系については, 定常蛍光分光と数値シミュレーションによるワイヤ内励起子ホッピングの新実証法の提案も行った. これは, これは太陽光の有効活用にも資する知見・特性である.

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

• [Int'l Joint Research] University of Bremen(ドイツ)
• [Journal Article] Aurophilicity and Photoluminescence of (6-Diphenylpnicogenoacenaphth-5-yl)gold Compounds (2019)
  • Author(s): Do Truong Giang、Hupf Emanuel、Lork Enno、Koegel Julius F.、Mohr Fabian、Brown Alex、Toyoda Ryojun、Sakamoto Ryota、Nishihara Hiroshi、Mebs Stefan、Beckmann Jens
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2019 Issue: 5 Pages: 647-659
  • DOI: 10.1002/ejic.201801190
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A single-stranded coordination copolymer affords heterostructure observation and photoluminescence intensification (2019)
  • Author(s): Ryojun Toyoda, Ryota Sakamoto, Naoya Fukui, Ryota Matsuoka, Mizuho Tsuchiya, Hiroshi Nishihara
  • Journal Title: Sci. Adv. Volume: 5 Issue: 1
  • DOI: 10.1126/sciadv.aau0637
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Expansion of the Graphdiyne Family: A Triphenylene-Cored Analogue (2018)
  • Author(s): Matsuoka Ryota、Toyoda Ryojun、Shiotsuki Ryo、Fukui Naoya、Wada Keisuke、Maeda Hiroaki、Sakamoto Ryota、Sasaki Sono、Masunaga Hiroyasu、Nagashio Kosuke、Nishihara Hiroshi
  • Journal Title: ACS Applied Materials & Interfaces Volume: 10 Issue: 3 Pages: 2730-2733
  • DOI: 10.1021/acsami.8b00743
  • Peer Reviewed
• [Journal Article] A pyrazine-incorporated graphdiyne nanofilm as a metal-free electrocatalyst for the hydrogen evolution reaction (2018)
  • Author(s): Sakamoto Ryota、Shiotsuki Ryo、Wada Keisuke、Fukui Naoya、Maeda Hiroaki、Komeda Joe、Sekine Ryosuke、Harano Koji、Nishihara Hiroshi
  • Journal Title: Journal of Materials Chemistry A Volume: 6 Issue: 44 Pages: 22189-22194
  • DOI: 10.1039/c8ta07347c
  • Peer Reviewed
• [Journal Article] Three-dimensional graphdiyne as a topological nodal-line semimetal (2018)
  • Author(s): Takafumi Nomura, Tetsuro Habe, Ryota Sakamoto, Mikito Koshino
  • Journal Title: Physical Review Materials Volume: 2 Issue: 5 Pages: 054204-054204
  • DOI: 10.1103/physrevmaterials.2.054204
  • Peer Reviewed
• [Journal Article] Oxidation-Promoted Interfacial Synthesis of Redox-Active Bis(diimino)nickel Nanosheet (2018)
  • Author(s): Eunice J H Phua, Kuo-Hui Wu, Keisuke Wada, Tetsuro Kusamoto, Hiroaki Maeda, Jian Cao, Ryota Sakamoto, Hiroyasu Masunaga, Sono Sasaki, Jia-Wei Mei, Wei Jiang, Feng Liu, Hiroshi Nishihara
  • Journal Title: Chemistry Letters Volume: 47 Issue: 2 Pages: 126-129
  • DOI: 10.1246/cl.170928
  • NAID: 130006337769
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Dibenzopyrrolo[1,2-a][1,8]naphthyridines: Synthesis and Structural Modification of Fluorescent L-Shaped Heteroarenes (2017)
  • Author(s): Tateno Kotaro、Ogawa Rie、Sakamoto Ryota、Tsuchiya Mizuho、Kutsumura Noriki、Otani Takashi、Ono Kosuke、Kawai Hidetoshi、Saito Takao
  • Journal Title: The Journal of Organic Chemistry Volume: 83 Issue: 2 Pages: 690-702
  • DOI: 10.1021/acs.joc.7b02674
  • Peer Reviewed
• [Journal Article] Bis(dipyrrinato)zinc(II) Complex Chiroptical Wires: Exfoliation into Single Strands and Intensification of Circularly Polarized Luminescence (2017)
  • Author(s): Aoki Risa、Toyoda Ryojun、Koegel Julius F.、Sakamoto Ryota、Kumar Jatish、Kitagawa Yasutaka、Harano Koji、Kawai Tsuyoshi、Nishihara Hiroshi
  • Journal Title: Journal of the American Chemical Society Volume: 139 Issue: 45 Pages: 16024-16027
  • DOI: 10.1021/jacs.7b07077
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] β-IminoBODIPY oligomers: facilely accessible π-conjugated luminescent BODIPY arrays (2017)
  • Author(s): Tsuchiya Mizuho、Sakamoto Ryota、Shimada Masaki、Yamanoi Yoshinori、Hattori Yohei、Sugimoto Kunihisa、Nishibori Eiji、Nishihara Hiroshi
  • Journal Title: Chemical Communications Volume: 53 Issue: 54 Pages: 7509-7512
  • DOI: 10.1039/c7cc03279j
  • Peer Reviewed
• [Journal Article] Mechano-, thermo-, solvato-, and vapochromism in bis(acetato-κ1O)[4′-(4-(diphenylamino)phenyl)](2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)zinc(ii) and its polymer (2017)
  • Author(s): Tsukamoto Takamasa、Aoki Risa、Sakamoto Ryota、Toyoda Ryojun、Shimada Masaki、Hattori Yohei、Kitagawa Yasutaka、Nishibori Eiji、Nakano Masayoshi、Nishihara Hiroshi
  • Journal Title: Chemical Communications Volume: 53 Issue: 70 Pages: 9805-9808
  • DOI: 10.1039/c7cc05022d
  • Peer Reviewed