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2016 Fiscal Year Annual Research Report

Development of Novel Photo- and Electro-functional Polymers by SOMO Design of Organic Radicals

Research Project

Project/Area Number 24225003
Research InstitutionWaseda University

Principal Investigator

西出 宏之  早稲田大学, 理工学術院, 教授 (90120930)

Co-Investigator(Kenkyū-buntansha) 小柳津 研一  早稲田大学, 理工学術院, 教授 (90277822)
錦谷 禎範  早稲田大学, 理工学術院, 教授(任期付) (50708625)
Project Period (FY) 2012-05-31 – 2017-03-31
Keywords高分子化学 / 機能性高分子 / 有機ラジカル / 蓄電 / 光電変換 / 電荷輸送 / 電子交換 / 有機エレクトロニクス
Outline of Annual Research Achievements

有機安定ラジカル種のSOMO(Singly Occupied MO)が関与する可逆かつ速い電子授受にはじめて着目し、世界に先駆け合成してきたラジカルポリマー群による高速電荷輸送と高密度電荷貯蔵の発見とその解釈を起点として、電子交換反応に基づく導電・蓄電物質の基礎科学を描象することを目的とした。大流束電荷輸送系の創出とヘテロ接合を用いた流束制御を基軸とした現象の普遍化と、有機ラジカル種の拡充によるさらなる高速化やpnバイポーラ性など新規物性も活用してSOMO-π共役複合系へと一般化する道筋で、効率高い光電変換など有機物性機能の新領域を開拓した。平成28年度の主な実績は以下である。
(1)ラジカルポリマー/液相界面の構築と効率高い電荷分離・輸送を実現するため、印加電圧に依存し電気化学応答する界面、界面構造とレドックス能の相関などを解明した。また電解液に液晶分子を共存させ、ラジカルポリマー層の表面電荷に基づく液晶配向をイオン電導のスイッチングおよび伝導の異方性につなげた。
(2)SOMO関与の光電荷分離を精密合成された色素系へ展開し、ラジカルとの界面を分子レベルの電荷分離の場とする光電変換を実証した。10%超えの光電変換を分子構造との相関で体系化し、ラジカルによる光電変換素子として提示した。
(3)有機負極活物質として有用性を見い出したフルオレノンポリマーゲルの可逆的な負電荷貯蔵を水素付加体を与える電解水素化に拡張実験し、水素発生のサイクルが高分子の場で進行することを定量した。従来にない高分子水素キャリアとして可能性を提示した。
以上を総合して、SOMO制御に関する基本的手法を確立し、新しい光・電子機能性ポリマーとして取りまとめ、新型太陽電池や次世代蓄電地など実デバイスに波及する実践的化学として整理した。

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

    (20 results)

All 2017 2016

All Journal Article (14 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 14 results,  Open Access: 14 results) Presentation (6 results) (of which Int'l Joint Research: 4 results,  Invited: 3 results)

  • [Journal Article] Quantifying TEMPO Redox Polymer Charge Transport Towards the Organic Radical Battery2017

    • Author(s)
      C. Karlsson, T. Suga, H. Nishide
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: 9 Pages: 10692-10698

    • DOI

      10.1021/acsami.7b00403

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis of Dimethyl-Substituted Polyviologen and Control of Charge Transport in Electrodes for High-Resolution Electrochromic Displays2017

    • Author(s)
      K. Sato, R. Mizukami, T. Mizuma, H. Nishide, K. Oyaizu
    • Journal Title

      Polymers

      Volume: 9 Pages: 86

    • DOI

      10.3390/polym9030086

    • Peer Reviewed / Open Access
  • [Journal Article] Charge-Discharge with Rocking-Chair-Type Li+ Migration Characteristics in a Zwitterionic Radical Copolymer Composed of TEMPO and Trifluoromethanesulfonylimide with Carbonate Electrolytes for a High-Rate Li-Ion Battery2017

    • Author(s)
      H. Tokue, T. Murata, H. Agatsuma, H. Nishide, K. Oyaizu
    • Journal Title

      Macromolecules

      Volume: 50 Pages: 1950-1958

    • DOI

      10.1021/acs.macromol.6b02404

    • Peer Reviewed / Open Access
  • [Journal Article] Low‐Cost, Organic Light‐Emitting Electrochemical Cells with Mass‐Producible Nanoimprinted Substrates Made Using Roll‐to‐Roll Methods2017

    • Author(s)
      K. Sato, S. Uchida, S. Toriyama, S. Nishimura, K. Oyaizu, H. Nishide, Y. Nishikitani
    • Journal Title

      Advanced Materials Technologies

      Volume: - Pages: 1-8

    • DOI

      10.1002/admt.201600293

    • Peer Reviewed / Open Access
  • [Journal Article] Redox Mediation through TEMPO-Substituted Polymer with Nanogap Electrodes for Electrochemical Amplification2017

    • Author(s)
      H. Tokue, K. Kakitani, H. Nishide, K. Oyaizu
    • Journal Title

      Chemistry Letters

      Volume: 46 Pages: 647-650

    • DOI

      http://dx.doi.org/10.1246/cl.170055

    • Peer Reviewed / Open Access
  • [Journal Article] A Hydrogen Storable Quinaldine Polymer: Its Ni‐Electrodeposition‐assisted Hydrogenation and Subsequent Hydrogen Evolution2017

    • Author(s)
      R. Kato, T. Oya, Y. Shimazaki, K. Oyaizu, H. Nishide
    • Journal Title

      Polymer International

      Volume: 66 Pages: 647-652

    • DOI

      10.1002/pi.5327

    • Peer Reviewed / Open Access
  • [Journal Article] Electrochemical Current Rectification with Cross Reaction at a TEMPO/viologen-substituted Polymer thin-layer Heterojunction2016

    • Author(s)
      H Tokue, K Kakitani, H Nishide, K Oyaizu
    • Journal Title

      RSC Advances

      Volume: 6 Pages: 99195-99201

    • DOI

      10.1039/C6RA23124A

    • Peer Reviewed / Open Access
  • [Journal Article] A Ketone/alcohol Polymer for Cycle of Electrolytic Hydrogen-fixing with Water and Releasing under Mild Conditions2016

    • Author(s)
      R. Kato, K. Yoshimasa, T. Egashira, T. Oya, K. Oyaizu, H. Nishide
    • Journal Title

      Nature Communications

      Volume: 7 Pages: 1-7

    • DOI

      10.1038/ncomms13032

    • Peer Reviewed / Open Access
  • [Journal Article] Effect of π-Conjugated Polyelectrolyte on Performance of White Polymer Light-Emitting Diodes Based on Excitons and Exciplexes Having Long Intermolecular Distances2016

    • Author(s)
      Y. Nishikitani, N. Inokuchi, H. Nishide, S. Uchida, T. Shibanuma, S. Nishimura
    • Journal Title

      J. Phys. Chem. C

      Volume: 120 Pages: 13976-13986

    • DOI

      10.1021/acs.jpcc.6b04413

    • Peer Reviewed / Open Access
  • [Journal Article] Metallopolyyne Polymers with Ferrocenyl Pendant Ligands as Cathode-active Materials for Organic Battery Application2016

    • Author(s)
      Z. Meng, K. Sato, T. Sukegawa, K. Oyaizu, CL. Ho, J. Xiang, YH. Feng, YH. Lo, H. Nishide, WY. Wong
    • Journal Title

      J. Org. Chem.

      Volume: 812 Pages: 51-55

    • DOI

      10.1016/j.jorganchem.2015.11.019

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] A Quasi-Solid State DSSC with 10.1% Efficiency through Molecular Design of the Charge-Separation and-Transport2016

    • Author(s)
      M. Suzuka, N. Hayashi, T. Sekiguchi, K. Sumioka, M. Takata, N. Hayo, H. Ikeda, K. Oyaizu, H. Nishide
    • Journal Title

      Scientific Reporys

      Volume: 6 Pages: 28022

    • DOI

      10.1038/srep28022

    • Peer Reviewed / Open Access
  • [Journal Article] Poly (norbornyl-NDIs) as a Potential Cathode-active Material in Rechargeable Charge Storage Devices2016

    • Author(s)
      Y. Sasada, SJ. Langford, K. Oyaizu, H. Nishide
    • Journal Title

      RSC Adv.

      Volume: 6 Pages: 42911-42916

    • DOI

      10.1039/C6RA06103F

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Enhanced Catalytic Activity of Oxovanadium Complexes in Oxidative Polymerization of Diphenyl Disulfide2016

    • Author(s)
      F. Aida, Y. Takatori, D. Kiyokawa, K. Nagamatsu, K. Oyaizu, H. Nishide
    • Journal Title

      Polym. Chem.

      Volume: 7 Pages: 2087-2091

    • DOI

      10.1039/C5PY01980J

    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis and Charge-Discharge Properties of Organometallic Copolymers of Ferrocene and Triphenylamine as Cathode Active Materials for Organic-Battery Applications2016

    • Author(s)
      J. Xiang, K. Sato, H. Tokue, K. Oyaizu, CL. Ho, H. Nishide, WY. Wong, MD. Wei
    • Journal Title

      Euro. J. Inorg, Chem.

      Volume: - Pages: 1030-1035

    • DOI

      10.1002/ejic.201501169

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] Charge transport kinetics in a robust radical-substituted polymer/nanocarbon composite electrode2017

    • Author(s)
      佐藤歓
    • Organizer
      APS March Meeting 2017
    • Place of Presentation
      アメリカ、ルイジアナ
    • Year and Date
      2017-03-13 – 2017-03-16
    • Int'l Joint Research
  • [Presentation] An Alcohol Polymer for Safe and Clean Hydrogen-Storage and -Release2016

    • Author(s)
      西出宏之
    • Organizer
      International Symposium of Innovation on Polymer Science and Technology
    • Place of Presentation
      インドネシア、メダン
    • Year and Date
      2016-11-08
    • Int'l Joint Research / Invited
  • [Presentation] An Alcohol Polymer for Safe and Clean Hydrogen-Storage and -Release2016

    • Author(s)
      西出宏之
    • Organizer
      International Conference on Advanced Polymeric Materials
    • Place of Presentation
      韓国、済州
    • Year and Date
      2016-10-06
    • Int'l Joint Research / Invited
  • [Presentation] Polymers for Electrochemical Energy-Storage and Signal-Amplification Devices2016

    • Author(s)
      小柳津研一
    • Organizer
      International Conference on Advanced Polymeric Materials
    • Place of Presentation
      韓国、済州
    • Year and Date
      2016-10-05
    • Int'l Joint Research / Invited
  • [Presentation] ラジカルポリマー/SWNT 複合電極の作製と全有機二次電池への適用2016

    • Author(s)
      佐藤歓
    • Organizer
      平成28年度繊維学会年次大会
    • Place of Presentation
      日本、東京
    • Year and Date
      2016-06-08 – 2016-06-10
  • [Presentation] Dynamic Switching of Nematic/Cholesteric/Smectic Liquid Crystals by Reverside Redox Reactions of Radical Polymer2016

    • Author(s)
      佐藤歓
    • Organizer
      第65回高分子学会年次大会
    • Place of Presentation
      日本、神戸
    • Year and Date
      2016-05-25 – 2016-05-27

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Published: 2018-01-16  

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