Construction of assembled aromatic ring systems aimed for the organic electrochromic materials

• Project/Area Number: 25810019
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Shinshu University
• Principal Investigator: SHOJI Taku 信州大学, 学術研究院理学系, 助教 (60581014)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2015: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2014: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2013: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: アズレン / フェロセン / アリールアミン / 環化付加反応 / ドナー・アクセプターシステム / サイクリックボルタンメトリー / エレクトロクロミズム / アリールアズレン / 1,2'-ビアズレン / クロスカップリング反応

Outline of Final Research Achievements

Novel aromatic compounds based on donor-acceptor systems were prepared by the [2+2]cycloaddition-retroelectrocyclization sequence of alkyne derivatives with tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane in good to excellent yield. Intramolecular CT absorption bands were found in UV/Vis spectra of the TCBD and DCNQ chromophores. Analyses by CV and DPV showed that the TCBD and DCNQ chromophores exhibited a reversible multi-stage reduction wave. TCBD and DCNQ derivatives exhibited significant color changes with high reversibility, attributable to the stabilization of anionic species during the electrochemical reaction.

Research Products

• [Journal Article] Synthesis of 1,2’-Biazulenes by Palladium-Catalyzed Unusual Homo-coupling Reaction of 1-Haloazulenes in the Presence of Ferrocene (2016)
  • Author(s): Taku Shoji,* Kanami Miyashita, Takanori Araki, Miwa Tanaka, Akifumi Maruyama, Ryuta Sekiguchi, Shunji Ito, Tetsuo Okujima
  • Journal Title: SYNTHESIS Volume: 48 Issue: 15 Pages: 2438-2448
  • DOI: 10.1055/s-0035-1561418
  • NAID: 120007100282
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Properties of (3-Phenyl-1-azulenyl)tetracyanobetadienes and Tris(aryltetracyanobetadiene)s Connected with 1,3,5-Tri(1-azulenyl)benzene Core (2016)
  • Author(s): Taku Shoji,* Akifumi Maruyama, Miwa Tanaka, Daichi Nagai, Erika Shimomura, Kunihide Fujimori, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Masafumi Yasunami
  • Journal Title: ChemistrySelect Volume: 1 Issue: 1 Pages: 49-56
  • DOI: 10.1002/slct.201500036
  • NAID: 120007100281
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 2- and 6-thienylazulenes by palladium-catalyzed direct arylation of 2- and 6-haloazulenes with thiophene derivatives (2015)
  • Author(s): Taku Shoji,* Akifumi Maruyama, Takanori Araki, Shunji Ito and Tetsuo Okujima
  • Journal Title: Organic & Biomolecular Chemistry Volume: 13 Issue: 40 Pages: 10191-10197
  • DOI: 10.1039/c5ob01317h
  • NAID: 120007100278
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Properties and Redox Behavior of Ferrocenyl-1,1,4,4-tetracyano-1,3-butadienes Connected by Arylamine and Azobenzene Spacers (2015)
  • Author(s): Taku Shoji,* Natsumi Kamata, Akifumi Maruyama, Shunji Ito, and Tetsuo Okujima
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 88 Issue: 9 Pages: 1338-1346
  • DOI: 10.1246/bcsj.20150165
  • NAID: 130005099087
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Properties and Redox Behavior of Tris[1-azulenyltetracyanobetadiene and 1-azulenylbis(tetracyanobetadiene)s] Connected with 1,3,5-Tri(1-azulenyl)benzene Core (2015)
  • Author(s): Taku Shoji,* Akifumi Maruyama, Erika Shimomura, Daichi Nagai, Shunji Ito, Tetsuo Okujima, and Kozo Toyota
  • Journal Title: European Journal of Organic Chemistry Volume: 2015 Issue: 9 Pages: 1979-1990
  • DOI: 10.1002/ejoc.201403556
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 2,6-Diaminoazulenes by the SNAr Reaction with Cyclic Amines (2015)
  • Author(s): Taku Shoji,* Yuki Fujiwara, Akifumi Maruyama, Mitsuhisa Maruyama, Shunji Ito, Masafumi Yasunami, Ryuji Yokoyama, Noboru Morita
  • Journal Title: Heterocycles Volume: 90 Issue: 1 Pages: 85-88
  • DOI: 10.3987/com-14-s(k)1
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Properties and Redox Behavior of 1,1,4,4-Tetracyano-2-ferrocenyl-1,3-butadienes Connected by Aryl, Biaryl and Teraryl Spacers (2015)
  • Author(s): Taku Shoji,* Akifumi Maruyama, Chisa Yaku, Natsumi Kamata, Shunji Ito, Tetsuo Okujima and Kozo Toyota
  • Journal Title: Chemistry - A European Journal Volume: 21 Issue: 1 Pages: 402-409
  • DOI: 10.1002/chem.201405004
  • NAID: 120007100279
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 2-Aryl- and 6-Heteroaryl-1,3-di(4-pyridyl)azulenes by Katritzky’s Pyridylation of 2-Aryl- and 6-Heteroarylazulenes (2014)
  • Author(s): Taku Shoji,* Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Masafumi Yasunami, Junya Higashi, and Noboru Morita
  • Journal Title: Heterocycles Volume: 89 Issue: 11 Pages: 2588-2603
  • DOI: 10.3987/com-14-13102
  • NAID: 120007100269
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 1,3-Bis(tetracyano-2-azulenyl-3-butadienyl)azulenes by the [2 + 2] Cycloaddition-Retroelectrocyclization of 1,3-Bis(azulenylethynyl)azulenes with Tetracyanoethylene (2014)
  • Author(s): Taku Shoji,* Mitsuhisa Maruyama, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota
  • Journal Title: Chemistry - A European Journal Volume: 20 Issue: 37 Pages: 11903-11912
  • DOI: 10.1002/chem.201402939
  • NAID: 120007100277
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of 2,2’-Diamino-1,1’-biazulenes by the Copper-Catalyzed Homo-Coupling Reaction of 2-Aminoazulenes (2014)
  • Author(s): Taku Shoji,* Akifumi Maruyama, Atsuyo Yamamoto, Yuki Fujiwara, Shunji Ito, Tetsuo Okujima, Noboru Morita
  • Journal Title: Chemistry Letters Volume: 43 Issue: 7 Pages: 1122-1124
  • DOI: 10.1246/cl.140333
  • NAID: 130004868280
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Properties of 6-Methoxy- and 6-Dimethylamino-1-methylthio- and 1,3-Bis(methylthio)azulenes and Triflic Anhydride-Mediated Synthesis of Their Biaryl Derivatives (2014)
  • Author(s): Taku Shoji,* Akifumi Maruyama, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima, Junya Higashi, Kozo Toyota, Noboru Morita
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 87 Issue: 1 Pages: 141-154
  • DOI: 10.1246/bcsj.20130275
  • NAID: 130004153257
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Properties, and Crystal Structure of DDQ-Adducts of Ethynylated 2H-Cyclohepta[b]furan-2-ones (2014)
  • Author(s): Taku Shoji,* Mitsuhisa Maruyama, Erika Shimomura, Akifumi Maruyama, Shunji Ito, Masafumi Yasunami, Junya Higashi, Kozo Toyota, and Noboru Morita*
  • Journal Title: Heterocycles Volume: 88 Issue: 1 Pages: 319-329
  • DOI: 10.3987/com-13-s(s)24
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Properties and Redox Behavior of Ene-Diyne Scaffolds Bearing 1- and 2-Azulenyl groups at the Periphery (2013)
  • Author(s): Taku Shoji,* Erika Shimomura, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima, Noboru Morita
  • Journal Title: European Journal of Organic Chemistry Volume: なし Issue: 5 Pages: 957-964
  • DOI: 10.1002/ejoc.201201397
  • NAID: 120007100276
  • Peer Reviewed
• [Journal Article] Synthesis of 2-Azulenyl-1,1,4,4-tetracyano-3-ferrocenyl-1,3-butadienes by the [2+2] Cycloaddition of (Ferrocenylethynyl)azulenes with Tetracyanoethylene (2013)
  • Author(s): Taku Shoji,* Shunji Ito, Tetsuo Okujima, Noboru Morita
  • Journal Title: Chemistry - A European Journal Volume: 19 Issue: 18 Pages: 5721-5730
  • DOI: 10.1002/chem.201202257
  • NAID: 120007100274
  • Peer Reviewed
• [Journal Article] Synthesis of Novel Thiophene-fused 1,1’-Biazulene Derivative by the Reaction of Azuleno[1,2-b]thiophene with N-Iodosuccinimide (2013)
  • Author(s): Taku Shoji,* Erika Shimomura, Yuta Inoue, Mitsuhisa Maruyama, Atsuyo Yamamoto, Kunihide Fujimori, Shunji Ito, Masafumi Yasunami, Noboru Morita
  • Journal Title: Heterocycles Volume: 87 Issue: 2 Pages: 303-306
  • DOI: 10.3987/com-12-12638
  • NAID: 120007114366
  • Peer Reviewed
• [Journal Article] Synthesis of 1,6’-Bi- and 1,6’:3,6’’-Terazulenes from 1-Pyridyl- and 1,3-Di(pyridyl)azulenes by the Zieglar-Hafner Method (2013)
  • Author(s): Taku Shoji,* Atsuyo Yamamoto, Erika Shimomura, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota and Noboru Morita
  • Journal Title: Chemistry Letters Volume: 42 Issue: 6 Pages: 638-640
  • DOI: 10.1246/cl.130157
  • NAID: 10031176034
  • Peer Reviewed
• [Journal Article] Synthesis and Properties of Azulene-substituted Donor-Acceptor Chromophores Connected by Arylamine Cores (2013)
  • Author(s): Taku Shoji,* Erika Shimomura, Mitsuhisa Maruyama, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Noboru Morita
  • Journal Title: European Journal of Organic Chemistry Volume: なし Issue: 34 Pages: 7785-7799
  • DOI: 10.1002/ejoc.201301006
  • NAID: 120007100275
  • Peer Reviewed
• [Journal Article] Synthesis, Properties and Redox Behavior of Tetracyanobutadiene and Dicyanoquinodimethane Chromophores Bearing Two Azulenyl Substituents (2013)
  • Author(s): Taku Shoji,* Mitsuhisa Maruyama, Erika Shimomura, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Noboru Morita
  • Journal Title: The Journal of Organic Chemistry Volume: 78 Issue: 24 Pages: 12513-12524
  • DOI: 10.1021/jo402104n
  • Peer Reviewed
• [Presentation] Synthesis and Properties of Azulenyltetracyanobutadiene Oligomers connected with Triphenylamine (2015)
  • Author(s): Taku Shoji, Akifumi Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota
  • Organizer: 平成27年度化学系学協会東北大会
  • Place of Presentation: 弘前大学
  • Year and Date: 2015-09-12
• [Presentation] アゾベンゼンに連結したアズレニルテトラシアノブタジエン,ジシアノキノジメタン誘導体の合成研究 (2014)
  • Author(s): 永井 大地, 丸山 晃史, 庄子 卓
  • Organizer: 第45回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 中部大学 (愛知県春日井市)
  • Year and Date: 2014-11-30
• [Presentation] アリールアミン類に連結したフェロセニルテトラシアノブタジエンの合成と性質 (2014)
  • Author(s): 丸山 晃史, 鎌田 夏美, 庄子 卓
  • Organizer: 第45回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 中部大学 (愛知県春日井市)
  • Year and Date: 2014-11-30
• [Presentation] アリール基に連結したフェロセニルテトラシアノブタジエンの合成と酸化還元的挙動 (2014)
  • Author(s): 庄子卓, 丸山晃史, 夜久千紗, 鎌田夏美, 奥島鉄雄, 伊東俊司
  • Organizer: 平成26年度化学系学協会東北大会
  • Place of Presentation: 山形大学 (山形県米沢市)
  • Year and Date: 2014-09-20 – 2014-09-21
• [Presentation] 2-アミノアズレン類の触媒的C-H結合活性化によるアリール化反応の開発 (2014)
  • Author(s): 庄子卓, 丸山晃史, 藤原優紀, 山本昌, 奥島鉄雄, 伊東俊司
  • Organizer: 平成26年度化学系学協会東北大会
  • Place of Presentation: 山形大学 (山形県米沢市)
  • Year and Date: 2014-09-20 – 2014-09-21
• [Presentation] アリールアミンオリゴマーに連結したアズレニルテトラシアノブタジエンの合成と性質 (2014)
  • Author(s): 丸山晃史, 庄子卓
  • Organizer: 第25回基礎有機化学討論会
  • Place of Presentation: 東北大学 (宮城県仙台市)
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] ヘキサフェニルベンゼンに連結したアズレニルテトラシアノブタジエンクロモフォアの合成研究 (2013)
  • Author(s): 丸山 満久, 庄子 卓
  • Organizer: 第24回基礎有機化学討論会
  • Place of Presentation: 学習院大学
• [Presentation] Synthesis and Properties of 1,3,5-Tri(1-azulenyl)benzene Derivatives (2013)
  • Author(s): Taku Shoji, Akifumi Maruyama, Erika Shimomura, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima
  • Organizer: International Symposium for the 70th Anniversary of the Tohoku Branch of the Chemical Society of Japan
  • Place of Presentation: 東北大学
• [Presentation] Synthesis of Donor-Acceptor Type Azulene Derivatives from 1-Pyridylazulenes (2013)
  • Author(s): Taku Shoji, Atsuyo Yamomato, Mitsuhisa Maruyama, Shunji Ito, Tetsuo Okujima, Kozo Toyota, Noboru Morita
  • Organizer: International Symposium for the 70th Anniversary of the Tohoku Branch of the Chemical Society of Japan
  • Place of Presentation: 東北大学
• [Remarks] 信州大学学術オンラインシステムSOAR
  • URL: http://soar-rd.shinshu-u.ac.jp/profile/ja.gmShOakh.html
• [Remarks] Researchmap
  • URL: http://researchmap.jp/shoji-azulene
• [Remarks] ResearcherID
  • URL: http://www.researcherid.com/rid/J-5166-2013
• [Remarks] 信州大学 学術情報オンラインシステムSOAR
  • URL: http://soar-rd.shinshu-u.ac.jp/profile/ja.gmShOakh.html
• [Remarks] researchmap
  • URL: http://researchmap.jp/shoji-azulene
• [Remarks] 信州大学 学術情報オンラインシステムSOAR
  • URL: http://soar-rd.shinshu-u.ac.jp/profile/ja.gmShOakh.html