Synthesis of New π-Conjugated Polymers and Their Spin-Correlated Function

• Project/Area Number: 17067017
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Waseda University
• Principal Investigator: NISHIDE Hiroyuki Waseda University, 理工学術院, 教授 (90120930)
• Co-Investigator(Kenkyū-buntansha): TAKEMURA Ichiro 早稲田大学, 先進理工学部, 助手 (80454065)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥28,400,000 (Direct Cost: ¥28,400,000); Fiscal Year 2008: ¥4,800,000 (Direct Cost: ¥4,800,000); Fiscal Year 2007: ¥5,000,000 (Direct Cost: ¥5,000,000); Fiscal Year 2006: ¥8,500,000 (Direct Cost: ¥8,500,000); Fiscal Year 2005: ¥10,100,000 (Direct Cost: ¥10,100,000)
• Keywords: 高分子合成 / 高分子構造・物性 / 電子・電気材料 / ナノ材料 / スピンエレクトロロ二クス / スピンエレクトロニクス / 共役高分子 / らせん高分子 / ヘリセン / スルホニウム / 導電性 / 分子配向 / ポリイオンコンプレックス

Research Abstract

共役ポリマーは精密な分子形状に基づいて、剛直ならせん構造や分子間の組織体を自発的に形成する。有機ラジカルの不対電子を組み込んだ新しいπ共役ポリマーは、共役構造とスピンが相関してはじめて発現する電磁機能が期待される。本研究では、ベンゾチオフェンおよび芳香族フェニレンビニレン、トリフェニレン化合物を位置選択的に還元重合し、精密に制御された分子構造を有するポリマーを合成、階層的なπ共役系を介した有機不対電子の振る舞いを、電子移動過程や多スピン間の交換相互作用として解析した。共役ポリマーの高次構造と電子状態の相関をもとに、新しい電磁気、光磁気機能を開拓し、有機スピントロニクスなどπ電子相関科学に踏み込んだ。本研究の研究成果の概要を以下に記載するが、得られた成果の詳細は、公開シンポジウムおよび学会で口頭発表するとともに、以下に記載した学会誌・学術論文として公表した。

Research Products

• [Journal Article] Chiral Alkylated Poly(m-phenlene)s : Optical Activity and Thermal Stability of Helical Structure (2009)
  • Author(s): R. Sone, I. Takemura, K. Oyaizu, H. Nishide
  • Journal Title: Synth. Met 159 Pages: 925-930
  • Peer Reviewed
• [Journal Article] 2,6,10-Tris(bithiophenyl)triphenylene : Syntesis and High-Spin Alignment in its p-Doped Radical Derivative (2009)
  • Author(s): T. Ibe, H. Umeda, H. Nishide
  • Journal Title: Synth. Met. 59 Pages: 788-791
  • Peer Reviewed
• [Journal Article] Coupling Reaction on Gold Nanoparticle to Yield Polythiophene/Gold Nanoparticle Alternate Network Film (2009)
  • Author(s): M. Tanaka, R. Fujita, H. Nishide
  • Journal Title: Journal of Nanoscience and Nanotechnology 9 Pages: 634-639
  • Peer Reviewed
• [Journal Article] Intramolecular Through-Space Antiferromagnetic Interactions of Cross-Conjugated Aromatic Polyaminium R adical Gels (2009)
  • Author(s): T. Michinobu, M. Tanaka, J. Inui, H. Nishide
  • Journal Title: Journal of Nanoscience and Nanotechnology 9 Pages: 514-521
  • Peer Reviewed
• [Journal Article] 2,6,10-Tris(bithiophenyl)triphenylene : Synthesis and High-Spin Alignment in Itsp-Doped Radical Derivetive (2009)
  • Author(s): T. lbe, H. Umeda, H. Nishide
  • Journal Title: Synthetic Metals (In press)
  • Peer Reviewed
• [Journal Article] Chiral Alkylated Poly(m-phenylene)s : Optical Activity and Thermal Stability of Helical Structures (2009)
  • Author(s): R. Sone, I. Takemura, K. Oyaizu, H. Nishide
  • Journal Title: Synthetic Metals (In press)
  • Peer Reviewed
• [Journal Article] Nernstian Adsorbate-like BulkLayer of Organic Radical Polymers for High-Density Charge Strage Purposes (2008)
  • Author(s): K. Oyaizu, Y. Ando, H. Konishi, H. Nishide
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 14459-14461
  • Peer Reviewed
• [Journal Article] Totally Orgnic Polymer-Based Electrochromic Cell Using TEMPO-Substituted Polynorbornene asa Counter Electrode-Active Material (2008)
  • Author(s): Y. Takahashi, N. Hayashi, K. Oyaizu, K. Honda and H. Nishide
  • Journal Title: Polym. J. 40 Pages: 763-767
  • Peer Reviewed
• [Journal Article] Poly(thiaheterohelicene) Derived from te Long-alkylated Polysulfonium Precursor (2008)
  • Author(s): I. Takemura, R. Sone, H. Nishide
  • Journal Title: Polym. Adv. Technol. 19 Pages: 1092-1096
  • Peer Reviewed
• [Journal Article] A non-volatile, bistable, and rewritable memory device fabricated with poly(nitroxide radical) and silver salt layers (2008)
  • Author(s): Y. Yonekuta, K. Honda, H. Nishide
  • Journal Title: Polym. Adv. Technol. 19 Pages: 281-284
  • Peer Reviewed
• [Journal Article] Battery-Inspired Nonvolatile, and Rewritable Memory Architecture : a Radical Polymer-Based Organc Device (2008)
  • Author(s): Y. Yonekuta, K. Susuki, K. Oyaizu, K. Honda, H. Nishide
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 14128-14129
  • Peer Reviewed
• [Journal Article] Poly(thiaheterohelicene) Derived from the Long-alkylated Polysulfonium precursor (2008)
  • Author(s): I. Takemura, R. Sone, H. Nishide
  • Journal Title: Polymers for Advanced Technologies 19 Pages: 1092-1096
  • Peer Reviewed
• [Journal Article] Nernstian Adsorbate-like Bulk Layer'of Organic Radical Polymers for High-Density Charge Storage Purpos es (2008)
  • Author(s): K. Oyaizu, Y. Ando, H. Konishi, H. Nishide
  • Journal Title: Journal of the American Chemical Society 130 Pages: 14459-14461
  • Peer Reviewed
• [Journal Article] A non-voltile, Bistable, and Rewritable Memory Device Fabricated with Poly (nitroxide radical) and Silver Salt Layers (2008)
  • Author(s): Y. Yonekuta, K. Honda, H. Nishide
  • Journal Title: Polymers for Advanced Technologies 19 Pages: 281-284
  • Peer Reviewed
• [Journal Article] M. Tanaka, R. Fujita, H. Nishide (2007)
  • Author(s): M. Tanaka, R. Fujita, H. Nishide
  • Journal Title: Polymer 48 Pages: 5884-5888
  • Peer Reviewed
• [Journal Article] Triarylamine-bearing poly(1,4-phenyl envinylene) : facile preparation and its durable aminium polyradical (2007)
  • Author(s): T. Kurata, Y.-J. Pu, H. Nishide
  • Journal Title: Polym. J. 39 Pages: 675-683
  • Peer Reviewed
• [Journal Article] Conductive characteristics of radical-bearing polythiophenes using a microcomb-shaped electrode (2007)
  • Author(s): M. Tanaka, K. Hatta, T. Edura, K. Tsutsui, Y. Wada, H. Nishide
  • Journal Title: Polym. Adv. Technol. 18 Pages: 925-931
  • Peer Reviewed
• [Journal Article] Battery-lnspired, Nonvoltile, and Rewritable Memory Architecture: a Radical Polymer-Based Organic Device (2007)
  • Author(s): Y. Yonekuta, K. Oyaizu, K. Honda, H. Nishide
  • Journal Title: Journal of the American Chemical Society 129 Pages: 14128-14129
  • Peer Reviewed
• [Journal Article] Alternate Network Film of Thiol Group-Terminated Polythiophene and Gold Nanoparticle (2007)
  • Author(s): M. Tanaka, R. Fujita, H. Nishide
  • Journal Title: Polymer 48 Pages: 5884-5888
  • Peer Reviewed
• [Journal Article] An Unpaired Electron-Based Hole-Transporting Molecule: Triarylamine-Combined Nitroxide Radicals (2007)
  • Author(s): T. Kurata, K. Koshika, F. Kato, J. Kido, H. Nishide
  • Journal Title: Chemical Communications 28 Pages: 2986-2988
  • Peer Reviewed
• [Journal Article] Conductive Characteristics of Radical-Bearing Polythiophenes Using a Microcomb-Shaped Electrode (2007)
  • Author(s): M. Tanaka, K. Hatta, T. Edura, K. Tsutsui, Y. Wada, H. Nishide
  • Journal Title: Polymers for Advanced Technologies 18 Pages: 925-931
  • Peer Reviewed
• [Journal Article] Magnetic Force Microscopy as a New Toolto Evaluate Local Magnetization of Organic Radical Polymers (2006)
  • Author(s): M. Tanaka, Y. Saito, H. Nishide
  • Journal Title: Chem. Lett. 35 Pages: 1414-1415
  • Peer Reviewed
• [Journal Article] Nanometer-Sized Polyradical Particles: Organic Magnetic Dot Array Formed n a Silicon Microfabricated Substrate (2006)
  • Author(s): M. Tanaka, S. Imai, T. Tanii, Y. Numao, N. Shimamoto, I. Ohdomari, H. Nishde
  • Journal Title: J. Polym. Sci. : Part A : Polym. Chem. 45 Pages: 521-530
  • Peer Reviewed
• [Journal Article] 2,6,10-tris(dianisylaminium)-3,7,11-tris(hexyloy)triphenylene: A robust quartet molecule at room temperature (2006)
  • Author(s): E. Fukuzaki, H. Nishide
  • Journal Title: Org. Lett. 8 Pages: 1835-1838
  • Peer Reviewed
• [Journal Article] A High-Spin and Helical Organic Polyer : Poly{[4-(dianisylaminium)phenyl]acetylene} (2006)
  • Author(s): H. Murata, D. Miyajima, H. Nishide
  • Journal Title: Macromolecules 39 Pages: 6331-6335
  • Peer Reviewed
• [Journal Article] Room-temperature high-spin organic single molecle : Nanometer-sized and hyperbranched poly[1,2,(4)-phenylenevinyl eneanisylaminum] (2006)
  • Author(s): E. Fukuzaki, H. Nishide
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 996-1001
  • Peer Reviewed
• [Journal Article] 2,6,10-Tris(dianisylaminium)-3,7,11-Tris(hexyloxy)triphenylene : A Robust Quartet Molecule at Room Temperature (2006)
  • Author(s): E.Fukuzaki, H.Nishide
  • Journal Title: Organic Letters 8 Pages: 1835-1838
• [Journal Article] A High-Spin and Helical Organic Polymer : Poly{[4-(dianisylaminium)phenyl]acetylene} (2006)
  • Author(s): H.Murata, D.Miyajima, H.Nishide
  • Journal Title: Macromolecules 39 Pages: 6331-6335
• [Journal Article] Nanometer-Sized Polyradical Particles : Organic Magnetic Dot Array Formed on a Silicon Microfabricated Substrate (2006)
  • Author(s): M.Tanaka, S.Imai, T.Tanii, Y.Numao, N.Shimamoto, I.Ohdomari, H.Nishide
  • Journal Title: J. Polymer. Scince : Part A : Polymer Chemistry 45 Pages: 521-530
• [Journal Article] Magnetic Force Microscopy as a New Tool to Evaluate Local Magnetization of Organic Radical Polymers (2006)
  • Author(s): M.Tanaka, Y.Saito, H.Nishide
  • Journal Title: Chemistry Letters 35 Pages: 1414-1415
  • NAID: 10020135012
• [Journal Article] Room-Temperature High-Spin Organic Single Molecule : Nanometer-Sized and Hyperbranched Poly[1,2,(4)-phenylenevinyleneanisylaminium] (2006)
  • Author(s): E.Fukuzaki, H.Nishide
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 996-1001
• [Journal Article] Electro- and Magneto-Responsible Chiral Polymer (2005)
  • Author(s): T. Iwasaki, H. Nishide
  • Journal Title: Curr. Org. Chem. 9 Pages: 1665-1684
  • Peer Reviewed
• [Journal Article] A helical ladder polymer : Synthesis and Magnetic Circular Dichroism of Poly[phenylene-4,6-bis(methylsulfonio)- 1,3-diyl triflate] (2005)
  • Author(s): T. Iwasaki, K. Katayose, Y. Kohinata, H. Nishide
  • Journal Title: Polym. J. 37 Pages: 592-598
  • NAID: 10019038039
  • Peer Reviewed
• [Journal Article] Poly(thiaheterohelicene) : A Novel Siff Helical Polymer Comprised of Fused Benzothiophene Rings (2005)
  • Author(s): T. Iwasaki, Y. Kohinata, H. Nishide
  • Journal Title: Org. Lett. 7 Pages: 75-758
  • Peer Reviewed
• [Journal Article] Poly(thiaheterohelicene) : A Novel Stiff Helical Polymer Comprised of Fused Benzothiophene Rings (2005)
  • Author(s): T.Iwasaki, Y.Kohinata, H.Nishide
  • Journal Title: Org.Lett. 7 Pages: 755-758
• [Journal Article] Facile Preparation of Helical Ladder Polymer Composed of Fused Phenoxathiine Rings (2005)
  • Author(s): T.Iwasaki, Y.Tsukahara, H.Nishide
  • Journal Title: Chem.Lett. 34 Pages: 164-165
• [Journal Article] A Helical Ladder Polymer : Synthesis and Magnetic Circular Dichroism of Poly[phenylene-4,6-bis(methylsulfonio)-1,3-diyl triflate] (2005)
  • Author(s): T.Iwasaki, K.Katayose, Y.Kohinta, H.Nishide
  • Journal Title: Polymer.J. 37 Pages: 592-598
  • NAID: 10019038039
• [Journal Article] Electro- and Magneto-Responsible Chiral Polymers (2005)
  • Author(s): T.Iwasaki, H.Nishide
  • Journal Title: Curr.Org.Chem. 9 Pages: 1665-1685
• [Journal Article] Radical Polymers for Organic Electronic Devices: ARadical Departure from Conjugated Polymers?
  • Author(s): K. Oyaizu, H. Nishide
  • Journal Title: Adv. Mater. 21 Pages: 2339-2344
  • Peer Reviewed
• [Presentation] π-Conjugation-Inspired Functional Polymers with Densely Populated Unpaired Electrons (2008)
  • Author(s): H. Nishide
  • Organizer: 18th Iketani Conference
  • Place of Presentation: 淡路
  • Year and Date: 2008-10-28
• [Presentation] A Molecular Route to Unpaired Electron-Based Organic Devices (2008)
  • Author(s): H. Nishide
  • Organizer: Fujiwara Seminar 2008
  • Place of Presentation: 苫小牧
  • Year and Date: 2008-07-30
• [Presentation] Very High-Spin Organic Polymers Based on Hyperbranched 7r-conjugations (2008)
  • Author(s): H. Nishide. T. Ibe, E. Fukuzaki
  • Organizer: 2008 Spring Natinal ACS Meeting
  • Place of Presentation: New Orleans
  • Year and Date: 2008-04-06
• [Presentation] Organic Polymer-Based Batteries for a Biomedical Application (2008)
  • Author(s): H. Nishide
  • Organizer: International Symposium on Biomaterials
  • Place of Presentation: Sanya, China
• [Presentation] π-Conjugation-Inspired Functional Polymers with Densely Popuated Unpaired Electrons (2008)
  • Author(s): H. Nishide
  • Organizer: 18th Iketani Conference International Conference on ontrol of Super-Hierarchical Structures and Innovative Functions of Next-Generaion Conjugated Polymers
  • Place of Presentation: Awaji, Japan
• [Presentation] Radical Polymers Leading to Environmentally-Benign Organic-Baed Batteries (2008)
  • Author(s): H. Nishide
  • Organizer: 2nd IUPAC Conference on Green Chemistry Moscow-St
  • Place of Presentation: Moscow-St. Petersburg, Russia
• [Presentation] Radical Polymers for Organic-based Rechargeable Deice (2008)
  • Author(s): H. Nishide, K. Oyaizu
  • Organizer: 236th ACS National Meeting
  • Place of Presentation: Philadelphia, USA
• [Presentation] Radical Polymers Leading to Environmentally-Benign Organic-Baed Batteries, International Conference on Advanced and Sustainable Polymers (2008)
  • Author(s): H. Nishide
  • Organizer: International Conference on Advanced and Sustainable Polymers
  • Place of Presentation: Bandung, Indonesia
• [Presentation] A Molecular Route to Unpaired Electron-Based Organic Devices (2008)
  • Author(s): H. Nishide
  • Organizer: Fujiwara Seminar 2008 Molecular Magnetism
  • Place of Presentation: Tomakomai, Japan
• [Presentation] Assessing the Future of Printed Batteries (2008)
  • Author(s): H. Nishide
  • Organizer: Plastic Electronics Asia 2008
  • Place of Presentation: Seoul, Korea
• [Presentation] Radical Polymers for Organic-based Rechargeable Batteries (2008)
  • Author(s): H. Nishide
  • Organizer: International Symposium on Polymer Chemistry PC2008
  • Place of Presentation: Hefei, China
• [Presentation] Charge Transport within Radical Redox Polymers as Electroactive Materials in Thin Film Batteries (2008)
  • Author(s): H. Nishide
  • Organizer: Spring Meeting of te Membrane Society, Korea
  • Place of Presentation: Seoul, Korea
• [Presentation] Very High-Spin Organic Polymers Based on Hyperbranched π-Conjugations (2008)
  • Author(s): H. Nishide
  • Organizer: 235th ACS Nathinal Meeting
  • Place of Presentation: New Orleans, USA
• [Presentation] Radical Polymers Leading to Organic-Based Energy Devices (2007)
  • Author(s): H. Nishide
  • Organizer: International Symposium on Polymers for Advanced Technologies
  • Place of Presentation: Shanghai, China
  • Year and Date: 2007-10-22
• [Presentation] A Paper-like Polymer-Based Rechargeble Device (2007)
  • Author(s): H. Nishide
  • Organizer: ACS Symposium on Energy Storage
  • Place of Presentation: Boston, USA
  • Year and Date: 2007-08-22
• [Presentation] Radical Polymers Leading to Organic-Based Energy Devices, International Symposium on Polymers for Advanced Technologies (2007)
  • Author(s): H. Nishide
  • Place of Presentation: Shanghai, China
  • Year and Date: 2007-08-22
• [Presentation] Radical Polymer-Based Memory Devices (2007)
  • Author(s): H. Nishide
  • Organizer: East Asian Symposium on Polymers for Advanced Technologies
  • Place of Presentation: Li-Jiang, China
  • Year and Date: 2007-07-24
• [Presentation] Radical Polymers for Innovative Design of an Organic-Based Printable Battery (2007)
  • Author(s): H. Nishide
  • Organizer: International Symposium on Macromolecules for a Safe, Sustainable and Healthy World
  • Place of Presentation: New York, USA
  • Year and Date: 2007-06-12
• [Presentation] Radical Polymers for lnnovative Design of an Organic-Based Printable Battery (2007)
  • Author(s): H. Nishide
  • Organizer: International Symposium on Macromolecules for a Safe, Sustainable and Healthy World
  • Place of Presentation: New York, USA
  • Year and Date: 2007-06-12
• [Presentation] Radical Polymers Loading to Organic-Based Devices (2007)
  • Author(s): H. Nishide
  • Organizer: Annual Meeting of Polymer Society of Korea
  • Place of Presentation: Cheju, Korea
  • Year and Date: 2007-04-12
• [Presentation] Radical Polymers Leading to a Totally Organic-Based Battery (2006)
  • Author(s): H. Nishide
  • Organizer: 10th International Conference on Molecule-based Magnets
• [Presentation] Radical Polymers as a New Material for Battery (2006)
  • Author(s): H. Nishide
  • Organizer: 41th IUPAC International Symposium on Macromolecules-World Polymer Congress MACRO 2006
• [Presentation] Organic Radical Polymers as a New Class of Electrode-Active Materials (2005)
  • Author(s): H. Nishide
  • Organizer: Pacific Polymer Conference IX
• [Presentation] Radical Polymers : A New Material for Battery and Memory Device (2005)
  • Author(s): H. Nishide
  • Organizer: East Asian Symposium on Polymers for Advanced Technologies
• [Book] Advanced Nanomaterials (2009)
  • Author(s): K. E. Geckeler, H. Nishide
  • Total Pages: 360
  • Publisher: Weinheim
• [Book] Advanced Nanomaterials (2008)
  • Author(s): K. E. Geckeler, H. Nishide, Ed.
  • Total Pages: 728
  • Publisher: WILEY-VCH
• [Book] 「ナノ有機エレクトロニクス」第六章第二節「ナノ磁性ドット:有機ラジカルポリマーの分子設計と応用」 (2008)
  • Author(s): 伊部武史、西出宏之
  • Publisher: 工業調査会
• [Book] Elsevier, "Carbon-Based Magnetism", Chapter 3"Persistent High-Spin Organic Polyradicals" (2006)
  • Author(s): F. Palacio, T. Makarova, Ed.H. Murata, H. Nishide
• [Book] エヌ・ティー・エス,「電池革新が拓く次世代電源」第二章「有機ラジカル電池-原理と応用- (2006)
  • Author(s): 辰巳国昭 他,須賀健雄、西出宏之
• [Book] American Scientific Publisher, "Functional Nanomaterials" Chapter 12 "Arrangement of Polymer Nano-Particles on Micro- and Nano-Fabricated Silicon Substrates" (2005)
  • Author(s): M. Tanaka, H. Nishide K. E. Geckeler, E. Rosenberg, Ed.
• [Remarks]
  • URL: http://www.appchem.waseda.ac.jp/~polymer/