Linear Acene Proton Conductors for Molecular Protonics

• Project/Area Number: 15K13684
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Functional solid state chemistry
• Research Institution: National Institute for Materials Science
• Principal Investigator: HILL Jonathan 国立研究開発法人物質・材料研究機構, 国際ナノアーキテクトニクス研究拠点, 主席研究員 (30421431)
• Co-Investigator(Renkei-kenkyūsha): Labuta Jan 国立研究開発法人物質・材料研究機構, 国際ナノアーキテクトニクス研究拠点, 独立研究者 (00720690) ; Matsushita Yoshitaka 国立研究開発法人物質・材料研究機構, 技術開発・共用部門 材料分析ステーション 化学分析・X線回折グループ, グループリーダー (70422441) ; Wakayama Yutaka 国立研究開発法人物質・材料研究機構, 国際ナノアーキテクトニクス研究拠点 量子デバイス工学グループ, グループリーダー (00354332)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2017: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2016: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2015: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: Acene / Proton conductor / Pyrazinacene / Tautomerism

Outline of Final Research Achievements

A class of linear acenes containing up to 14 nitrogen atoms has been prepared. These are the longest ‘pyrazinacene’ compounds prepared to date. The compounds have been characterized by chemical methods and crystallography. If compounds contained reduced rings (i.e. have hydrogen atoms) they were found to be delocalized, as predicted. Several compounds were studied for self-assembly on surfaces and were found to form polymeric structures. Some of the compounds were found to be useful for solar cell applications. The compounds were also found to be highly useful as organic catalysts based on the presence of the exchangeable protons and photosensitivity, as discovered in this work.

Research Products

• [Journal Article] Phenanthroline-fused Pyrazinacenes: One-pot Synthesis, Tautomerization and a Ru(II)(2,2’-bpy)2 Derivative (2018)
  • Author(s): Pavel Svec, Whitney A. Webre, Gary J. Richards, Jan Labuta, Yutaka Wakayama, David Miklik, Paul A. Karr, Toshiyuki Mori, Katsuhiko Ariga, Francis D’Souza and Jonathan P. Hill
  • Journal Title: European Journal of Inorganic Chemistry Volume: - Issue: 22 Pages: 2541-2548
  • DOI: 10.1002/ejic.201800283
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structural Modulation of Chromic Response: Effects of Binding Site Blocking in a Conjugated Calix[4]pyrrole Chromophore (2018)
  • Author(s): Vaclav Brezina, Shinsuke Ishihara, Jan Lang, Lenka Hanykova, Katsuhiko Ariga, Jonathan P. Hill, Jan Labuta
  • Journal Title: ChemistryOpen Volume: - Issue: 5 Pages: 323-335
  • DOI: 10.1002/open.201800005
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Fluoride-ion-binding Promoted Photoinduced Charge Separation in a Self-assembled C60 Alkyl Cation Bound Bis-crown Ether-oxoporphyrinogen Supramolecule (2018)
  • Author(s): Whitney A. Webre, Habtom B. Gobeze, Shuai Shao, Paul A. Karr, Katsuhiko Ariga, Jonathan P. Hill, Francis D’Souza
  • Journal Title: Chemical Communications Volume: 54 Issue: 11 Pages: 1351-1354
  • DOI: 10.1039/c7cc09524d
• [Journal Article] Fluorescent mesomorphic pyrazinacenes (2016)
  • Author(s): Gary J. Richards; Shinsuke Ishihara; Jan Labuta; David Miklik; Toshiyuki Mori; Shinji Yamada; Katsuhiko Ariga; Jonathan P. Hill
  • Journal Title: J. Mater. Chem. C Volume: 4 Issue: 48 Pages: 11514-11523
  • DOI: 10.1039/c6tc04628b
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Presentation] Pyrazinacenes and Oxoporphyrinogens (2017)
  • Author(s): Jonathan P. Hill, David Miklik, Pavel Svec, Yoshitaka Matsushita, Jan Labuta, Shinsuke Ishihara, Francis D’Souza, Katsuhiko Ariga
  • Organizer: 231st Electrochemical Society Meeting
  • Int'l Joint Research / Invited
• [Presentation] Pyrazinacenes and Oxoporphyrinogens (2017)
  • Author(s): Jonathan P. Hill, David Miklik, Yoshitaka Matsushita, Jan Labuta, Katsuhiko Ariga
  • Organizer: Congress of the Slovak Chemical Society
  • Invited
• [Presentation] Pyrazinacenes, Porphyrins and Oxoporphyrinogens (2017)
  • Author(s): Jonathan P. Hill, Jan Labuta, Shinsuke Ishihara, David Miklik, Gary J. Richards and Katsuhiko Ariga
  • Organizer: International Conf. on Functional Nanomaterials and Nanotechnology
  • Invited
• [Presentation] Chiral Effects in Non-Chiral Porphyrin Monomers and Chiral Porphyrin Dimers (2016)
  • Author(s): Jonathan P. Hill, Jan Labuta, Takashi Uchihashi, Shinsuke Ishihara, and Katsuhiko Ariga
  • Organizer: Symmetry Festival 2016
  • Place of Presentation: Vienna University of Technology, Austria
  • Year and Date: 2016-07-18
  • Int'l Joint Research / Invited
• [Presentation] Porphyrin Clamp and Tripod for Surface Assemblies (2016)
  • Author(s): Jonathan P. Hill, Yongshu Xie, Misaho Akada, Yutaka Wakayama, Katsuhiko Ariga
  • Organizer: International Conference on Porphyrins and Phthalocyanines ICPP9
  • Place of Presentation: Nanjing, China
  • Year and Date: 2016-07-03
  • Int'l Joint Research / Invited
• [Presentation] Interactions of Antioxidant-substituted Macrocycles (2016)
  • Author(s): Jonathan P. Hill
  • Organizer: 229th Electrochemical Society Meeting
  • Place of Presentation: Hilton Hotel, San Diego, USA
  • Year and Date: 2016-05-29
  • Int'l Joint Research / Invited
• [Presentation] Porphyrins, Pyrazinacenes and Oxoporphyrinogens: Surface Assembly (and other) Effects (2015)
  • Author(s): Jonathan P. Hill, Yongshu Xie, Jan Labuta, Shinsuke Ishihara, Misaho Akada, Katsuhiko Ariga
  • Organizer: Western Pacific Colloids 2015
  • Place of Presentation: Angkor Borei Hotel, Siem Reap, Cambodia
  • Year and Date: 2015-11-15
  • Int'l Joint Research
• [Presentation] Porphyrins, Pyrazinacenes and Oxoporphyrinogens: Surface Assembly (and other) Effects (2015)
  • Author(s): Jonathan P. Hill, Jan Labuta, Gary J. Richards, Shinsuke Ishihara, Yongshu Xie, Francis D'Souza, Katsuhiko Ariga
  • Organizer: Schloss Dagstuhl Seminar 15402
  • Place of Presentation: Schloss Dagstuhl, University of Saarland, Germany
  • Year and Date: 2015-09-27
  • Invited
• [Presentation] Porphyrins and other Chromophores with Antioxidant Substituents (2015)
  • Author(s): Jonathan P. Hill, Shangbin Jin, Jan Labuta, Shinsuke Ishihara and Katsuhiko Ariga
  • Organizer: 227th Electrochemical Society Meeting
  • Place of Presentation: Hilton Hotel, Chicago, USA
  • Year and Date: 2015-05-24
  • Int'l Joint Research / Invited
• [Book] Tautomerism in Oxoporphyrinogens and Pyrazinacenes (2016)
  • Author(s): Jonathan P. Hill, Jan Labuta, Shinsuke Ishihara, Gary J. Richards, Yongshu Xie, Francis D'Souza, Katsuhiko Ariga
  • Total Pages: 25
  • Publisher: Wiley-VCH