Development of Novel Porphyrinoids with Heterole-fused Structure

• Project/Area Number: 15K17822
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: Higashino Tomohiro 京都大学, 工学研究科, 助教 (90711804)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: ポルフィリン / ピロール / 典型元素 / リン / チオフェン / ホスホール / ポルフィリノイド / 有機化学 / 典型元素化学

Outline of Final Research Achievements

We synthesized phosphole-fused porphyrin dimer for the first time as a representative of a new class of porphyrins with a phosphorus atom. This porphyrin dimer possesses excellent electron-accepting character. Then, we synthesized octaphyrins with a dithieno[3,4-b:3',4'-d]thiophene unit as thiophene-fused dithiaoctaphyrin. The octaphyrins revealed cross-conjugated and macrocyclic 36π-electron networks.
In addition, we synthesized dithieno[3,4-b:3',4'-d]phosphole derivatives as a new type of thiophene-fused phopholes. They exhibit the unique hybrid character of electron-withdrawing phosphole and electron-donating thiophene.

Research Products

• [Journal Article] Phosphole-Thiophene Hybrid: A Dual Role of Dithieno[3,4-b:3′,4′-d]phosphole as Electron Acceptor and Electron Donor (2018)
  • Author(s): Tomohiro Higashino, Keiichi Ishida, Takaharu Satoh, Yoshihiro Matano, Hiroshi Imahori
  • Journal Title: The Journal of Organic Chemistry Volume: 83 Issue: 6 Pages: 3397-3402
  • DOI: 10.1021/acs.joc.8b00030
  • Peer Reviewed
• [Journal Article] Hexaphyrin as a potential theranostic dye for photothermal therapy and 19F magnetic resonance imaging (2017)
  • Author(s): Tomohiro HIGASHINO, Hirotaka NAKATSUJI, Ryosuke FUKUDA, Haruki OKAMOTO, Hirohiko IMAI, Tetsuya Matsuda*, Hidehito TOCHIO, Masahiro SHIRAKAWA*, Nikolai V. TKACHENKO, Mitsuru HASHIDA, Tatsuya MURAKAMI*, and Hiroshi IMAHORI*
  • Journal Title: Chembiochem Volume: - Issue: 10 Pages: 951-959
  • DOI: 10.1002/cbic.201700071
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Synthesis of Partially meso-Free 2,3-Di(arylethynyl)porphyrins (2017)
  • Author(s): T. Higashino, Y. Ohashi, and H. Imahori
  • Journal Title: Chem. Lett. Volume: 46 Issue: 7 Pages: 976-978
  • DOI: 10.1246/cl.170350
  • NAID: 130005709495
  • Peer Reviewed
• [Journal Article] A Hydroxamic Acid Anchoring Group for Durable Dye-Sensitized Solar Cells Incorporating a Cobalt Redox Shuttle (2017)
  • Author(s): T. Higashino, Y. Kurumisawa, N. Cai, Y. Fujimori, Y. Tsuji, S. Nimura, D. Packwood, J. Park, and H. Imahori
  • Journal Title: ChemSusChem Volume: 10 Issue: 17 Pages: 3347-3351
  • DOI: 10.1002/cssc.201701157
  • Peer Reviewed
• [Journal Article] Photovoltaic Properties and Long-Term Durability of Porphyrin-Sensitized Solar Cells with Silicon-Based Anchoring Groups (2017)
  • Author(s): T. Higashino, S. Nimura, K. Sugiura, Y. Kurumisawa, Y. Tsuji, and H. Imahori
  • Journal Title: ACS Omega Volume: 2 Issue: 10 Pages: 6958-6967
  • DOI: 10.1021/acsomega.7b01290
  • Peer Reviewed / Open Access
• [Journal Article] Thiophene-fused dithiaoctaphyrins: π-system switching between cross-conjugated and macrocyclic π-networks (2017)
  • Author(s): Tomohiro Higashino, Atsushi Kumagai, Hiroshi Imahori
  • Journal Title: Chemical Communications Volume: 印刷中 Issue: 37 Pages: 5091-5094
  • DOI: 10.1039/c7cc01273j
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Fusing Porphyrins and Phospholes: Synthesis and Analysis of a Phosphorus-Containing Porphyrin (2016)
  • Author(s): T. Higashino, T. Yamada, T. Sakurai, S. Seki and H. Imahori
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 40 Pages: 12311-12315
  • DOI: 10.1002/anie.201607417
  • Peer Reviewed
• [Journal Article] Hybrid [5]Radialenes with Bispyrroloheteroles: New Electron-Donating Units (2015)
  • Author(s): Tomohiro Higashino, Hiroshi Imahori
  • Journal Title: Chemisty - A European Journal Volume: 21 Issue: 38 Pages: 13375-13381
  • DOI: 10.1002/chem.201501822
  • NAID: 120005672558
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] アクセプターおよびドナーの両性質を有するジチエノホスホールの合成 (2018)
  • Author(s): 石田圭一、東野智洋、今堀博
  • Organizer: 日本化学会第98春季年会
• [Presentation] ホスホール架橋ポルフィリンダイマーの合成と物性 (2018)
  • Author(s): 西村一晟、東野智洋、今堀博
  • Organizer: 日本化学会第98春季年会
• [Presentation] Synthesis of Thiophene-fused Thiahexaphyrin and Its Moebius Aromaticity (2018)
  • Author(s): Tomohiro Higashino, Atsushi Kumagai, Hiroshi Imahori
  • Organizer: 日本化学会第98春季年会
• [Presentation] Development of Porphyrinoids with Radialene-type Heteroles (2018)
  • Author(s): 東野智洋
  • Organizer: Reaxys Prize Clubシンポジウム in Japan 2018
  • Invited
• [Presentation] チオフェン縮環ジチアオクタフィリンの合成と物性 (2017)
  • Author(s): 熊谷篤、東野智洋、今堀博
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 横浜 慶應義塾大学日吉キャンパス
  • Year and Date: 2017-03-16
• [Presentation] チオフェン縮環ジチアオクタフィリンの酸化による共役系のスイッチングと光学特性の変化 (2017)
  • Author(s): 熊谷篤、東野智洋、今堀博
  • Organizer: 2017年光化学討論会
• [Presentation] 高耐久性トリエトキシシリル吸着基を導入した新規プッシュ-プル型ポルフィリンの合成と太陽電池特性 (2017)
  • Author(s): 二村晋平、東野智洋、今堀博
  • Organizer: 2017年光化学討論会
• [Presentation] 高耐久性ヒドロキサム酸吸着基を有する新規ポルフィリン色素の合成と色素増感太陽電池性能 (2017)
  • Author(s): 楜澤佑真、東野智洋、今堀博
  • Organizer: 2017年光化学討論会
• [Presentation] ホスホール縮環ポルフィリンダイマーの合成と物性 (2016)
  • Author(s): 東野智洋、山田智紀、今堀博
  • Organizer: 第27回基礎有機化学討論会
  • Place of Presentation: 広島 広島国際会議場
  • Year and Date: 2016-09-01
• [Presentation] ハイブリッド[5]ラジアレン骨格を有するビスピロロヘテロールの合成 (2016)
  • Author(s): 東野智洋、今堀博
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 京都 同志社大学京田辺キャンパス
  • Year and Date: 2016-03-24