development of molecular devices with organometallic pi-conjugated systems

• Project Area: Coordination Programming - Science of Molecular Superstructures for Chemical Devices
• Project/Area Number: 24108101
• 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: Tokyo Institute of Technology
• Principal Investigator: AKITA Munetaka 東京工業大学, 資源化学研究所, 教授 (50167839)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥9,750,000 (Direct Cost: ¥7,500,000、Indirect Cost: ¥2,250,000); Fiscal Year 2013: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2012: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
• Keywords: π共役系 / 分子デバイス / 有機金属化学 / STMブレイクジャンクション法 / 分子回路 / 分子ジャンクション / ポルフィリン / 分子素子

Research Abstract

For development of molecular circuits studies on molecular wire and junction based on coordination have been conducted.
Two-dimensional systems based on prophyrin motifs were prepared and their performance based on accumulated pi-conjugated systems has been evaluated. The unique behavior such as switching of luminescence properties by redox processes, tuning of wire-like behavior and QCM properties was observed by analysis of redox properties of the peripheral metal groups and electronic spectra.
Wire-like performance of organic and organometallic molecular wire was evaluated by the STM break-junction method. It has been found that the latter showed performance better than the former presumably because of the relative energetics of the Fermi level of the electrode (Au) and the HOMO level of the molecular wires.

Research Products

• [Journal Article] Zinc-porphyrins functionalized with redox-active metal peripherals: enhancement of dπ–pπ interaction leading to unique assembly and redox-triggered remote switching of fluorescence (2013)
  • Author(s): Masahito Murai, Manabu Sugimoto, and Munetaka Akita
  • Journal Title: Dalton Trans. Volume: 42 Issue: 45 Pages: 16108-16120
  • DOI: 10.1039/c3dt51675j
  • Peer Reviewed
• [Journal Article] Synthesis of Trinuclear Pd-Ru-Pd Porphyrin Complexes with Axially Ligated Pd Centers. Prominent Metal-to-Ligand Charge Transfer Band in the Visible Region. (2013)
  • Author(s): Yusuke Yasu, Akiko Inagaki, and Munetaka Akita
  • Journal Title: J. Organomet. Chem. Volume: 753 Pages: 48-54
  • DOI: 10.1016/j.jorganchem.2013.12.008
  • Peer Reviewed / Open Access
• [Journal Article] Enhanced Photocatalytic Activity ofα-Methylstyrene Oligomerization through Effective Metal-to-Ligand Charge-Transfer Localization on the Bridging Ligand (2012)
  • Author(s): Hiroyuki Nitadori, Takeshi Takahashi, Akiko Inagaki, and Munetaka Akita
  • Journal Title: Inorg. Chem. Volume: 51 Pages: 51-62
  • Peer Reviewed
• [Journal Article] Theoretical Study on the Photocyclization Mechanism of Diarylethenes with Transition Metal Substituents (2012)
  • Author(s): Makoto Hatakeyama, Satoshi Yokojima, Keiko Shinoda, Takashi Koike, Munetaka Akita and Shinichiro Nakamura
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 85 Pages: 679-686
  • NAID: 10030785196
  • Peer Reviewed
• [Journal Article] Color Change of Redox-active Organometallic Dithienylethene Complexes by Photochemical and Redox Processes (2012)
  • Author(s): Huifang Li, Takashi Koike, and Munetaka Akita
  • Journal Title: Dyes and Pigments Volume: 92 Pages: 854-860
  • Peer Reviewed
• [Journal Article] Extended Fluorochromism of Anthracene Trimers with a meta-Substituted Triphenylamine or Triphenylphosphine Core (2012)
  • Author(s): Z. Li
  • Journal Title: Chem. Asian J Volume: 7 Issue: 8 Pages: 1789-1794
  • DOI: 10.1002/asia.201200310
• [Journal Article] Isostructural M2L4 Molecular Capsules with Anthracene Shells : Synthesis, Crystal Structures, and Fluorescent Properties (2012)
  • Author(s): Z. Li, N. Kishi, K. Yoza, M. Akita, M. Yoshizawa
  • Journal Title: Chemistry - A European Journal Volume: 18 Issue: 27 Pages: 8358-8365
  • DOI: 10.1002/chem.201200155
  • Peer Reviewed
• [Journal Article] A Tubular Macrocycle from Covalently Linked Anthracenes and meta-Phenylene Spacers (2012)
  • Author(s): K. Hagiwara
  • Journal Title: Chem. Commun. Volume: 48 Issue: 62 Pages: 7678-7680
  • DOI: 10.1039/c2cc31383a
• [Presentation] Organometallic Molecular Wires with Porphyrin-linkers (2013)
  • Author(s): Masanori Ono, Kentaro Mishiba, Takashi Koike, Yuya Tanaka and Munetaka Akita
  • Organizer: International Symposium on Molecular Materials & Devices
  • Place of Presentation: 東京工業大学
• [Presentation] Visible-Light Driven Organometallic Catalysis (2012)
  • Author(s): Munetaka Akita
  • Organizer: 第２５回国際有機金属化学会議
  • Place of Presentation: リスボン（ポルトガル）
  • Year and Date: 2012-09-02
  • Invited
• [Presentation] Visible light-Driven Organometallic Catalysis (2012)
  • Author(s): Takashi Koike and Munetaka Akita
  • Organizer: Frontier 2012
  • Place of Presentation: レンヌ、フランス
• [Presentation] Photochromic Organometallics : Switching and Multi-color Chromism of Dithienylethene Complexes (2012)
  • Author(s): Munetaka Akita
  • Organizer: Symposium on Photoactive Synthetic Materials 2012 (SPASM2012)
  • Place of Presentation: ブロツワフ、ポーランド
• [Presentation] Molecular Devices Based on Carbon-rich Organometallics (2011)
  • Author(s): Munetaka Akita
  • Organizer: 2011 Inorganic Conference of the Royal Australian Chemical Institute and the New Zealand Institute of Chemistry (IC'11)
  • Place of Presentation: パース、オーストラリア
• [Remarks]
  • URL: http://www.res.titech.ac.jp/~smart/smartj.html
• [Remarks]
  • URL: http://www.res.titech.ac.jp/~smart/smartj.html