Synthesis and Functionality of Aromatic Hemiporphyrazines

• Project/Area Number: 24685009
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Partial Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: The Institute of Physical and Chemical Research
• Principal Investigator: MURANAKA Atsuya 独立行政法人理化学研究所, 内山元素化学研究室, 専任研究員 (20374902)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥26,260,000 (Direct Cost: ¥20,200,000、Indirect Cost: ¥6,060,000); Fiscal Year 2014: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2013: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2012: ¥16,510,000 (Direct Cost: ¥12,700,000、Indirect Cost: ¥3,810,000)
• Keywords: 芳香族性 / ヘミポルフィラジン

Outline of Final Research Achievements

18π-electron benziphthalocyanines, which can be regarded as an intermediate between hemiporphyrazine and phthalocyanine, have been synthesized for the first time. It was found that the aromaticity and near-infrared absorption of the benziphthalocyanines can be controlled by chemical modification and by variation of the solvent. Aromatic hemiporphyrazines and their metal complexes have been synthesized and their molecular structures, aromaticity, and optical properties have been clarified.

Research Products

• [Journal Article] In-plane Aromaticity in Cycloparaphenylene Dications: A Magnetic Circular Dichroism and Theoretical Study (2015)
  • Author(s): N. Toriumi, A. Muranaka, E. Kayahara, S. Yamago, and M. Uchiyama
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 1 Pages: 82-85
  • DOI: 10.1021/ja511320f
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Unraveling the Electronic Structure of Azolehemiporphyrazines: Direct Spectroscopic Observation of Magnetic Dipole Allowed Nature of the Lowest π-π* Transition of 20π-Electron Porphyrinoids (2014)
  • Author(s): A. Muranaka, S. Ohira, N. Toriumi, M. Hirayama, F. Kyotani, Y. Mori, D. Hashizume and M. Uchiyama
  • Journal Title: J. Phys. Chem. A Volume: 118 Issue: 25 Pages: 4415-4424
  • DOI: 10.1021/jp5001557
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis and Properties of Palladium(II) Complexes of Aromatic Hemiporphyrazines (2014)
  • Author(s): A. Muranaka, F. Kyotani, X. Ouyang, D. Hashizume, M. Uchiyama
  • Journal Title: J. Porphyrins Phthalocyanines Volume: 18 Issue: 10n11 Pages: 869-874
  • DOI: 10.1142/s1088424614500667
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 18π Tautomeric Benziphthalocyanine: A Functional Near-IR Dye with Tunable Aromaticity (2014)
  • Author(s): N. Toriumi, A. Muranaka, K. Hirano, K. Yoshida, D. Hashizume, M. Uchiyama
  • Journal Title: Angew. Chem. Int. Ed. Volume: 印刷中
  • Peer Reviewed
• [Presentation] 近赤外光を利活用するための有機 π 電子系化合物の開発 (2015)
  • Author(s): 村中 厚哉
  • Organizer: 日本化学会 第９５春季年会
  • Place of Presentation: 日本大学（船橋）
  • Year and Date: 2015-03-26 – 2015-03-29
  • Invited
• [Presentation] ベンジフタロシアニンが示す近赤外領域のソルバトクロミズム (2015)
  • Author(s): 鳥海 尚之・村中 厚哉・平野 圭一・吉田 健吾・内山 真伸
  • Organizer: 日本化学会 第９５春季年会
  • Place of Presentation: 日本大学（船橋）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Electronic Structure Analysis of Cyclic π-electron Molecules: Porphyrinoids and Cycloparaphenylenes (2014)
  • Author(s): Atsuya Muranaka
  • Organizer: The 2nd RIKEN-SJTU Workshop on Energy, Environment and Photonics
  • Place of Presentation: RIKEN (Wako)
  • Year and Date: 2014-11-17 – 2014-11-18
  • Invited
• [Presentation] 互変異性ベンジフタロシアニン：芳香族性を調節可能な機能性近赤外色素の開発 (2014)
  • Author(s): 鳥海 尚之・村中 厚哉・平野 圭一・吉田 健吾・内山 真伸
  • Organizer: 第40回反応と合成の進歩シンポジウム
  • Place of Presentation: 東北大学（仙台）
  • Year and Date: 2014-11-10 – 2014-11-11
• [Presentation] In-plane Aromaticity of [8]Cycloparaphenylene Dication: A Magnetic Circular Dichroism and Theoretical Study (2014)
  • Author(s): A. Muranaka, N. Toriumi, E. Kayahara, S. Yamago, M. Uchiyama
  • Organizer: International Symposium on the Synthesis and Application of Curved Organic π-Molecules and Materials (CURO-π)
  • Place of Presentation: Kyoto University (Uji)
  • Year and Date: 2014-10-19 – 2014-10-21
• [Presentation] Electronic Structure of Azolehemiporphyrazine (2014)
  • Author(s): A. Muranaka, S. Ohira, N. Toriumi, M. Hirayama, F. Kyotani, Y. Mori, D. Hashizume, M. Uchiyama
  • Organizer: Michinoku International Symposium on Porphyrins, Phthalocyanines and Functional π Molecules
  • Place of Presentation: Zao
  • Year and Date: 2014-10-13 – 2014-10-16
• [Presentation] Synthesis and Electronic Properties of 18π Aromatic Benziphthalocyanine (2014)
  • Author(s): A. Muranaka, N. Toriumi, K. Hirano, K. Yoshida, M. Uchiyama
  • Organizer: 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul
  • Year and Date: 2014-06-22 – 2014-06-27
  • Invited
• [Presentation] Tuning of Aromaticity and Near-IR Absorption of 18π Tautomeric Benziphthalocyanine (2014)
  • Author(s): N. Toriumi, A. Muranaka, K. Hirano, K. Yoshida, M. Uchiyama
  • Organizer: 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul
  • Year and Date: 2014-06-22 – 2014-06-27
• [Presentation] 18π互変異性ベンジフタロシアニン：芳香族性を調節可能な機能性近赤外色素の開発 (2014)
  • Author(s): 鳥海尚之・村中厚哉・平野圭一・吉田健吾・内山真伸
  • Organizer: 日本薬学会第１３４年会
  • Place of Presentation: 熊本大学（熊本）
• [Presentation] 化学反応によるベンジフタロシアニンの芳香族性の制御 ~ 6π vs. 18π ~ (2013)
  • Author(s): 鳥海尚之・平野圭一・内山真伸・京谷史子・吉田健吾・村中厚哉
  • Organizer: 第２４回基礎有機化学討論会
  • Place of Presentation: 学習院大学（東京）
• [Presentation] ベンジフタロシアニンの電子的性質と芳香族性の制御 (2013)
  • Author(s): 鳥海尚之・平野圭一・内山真伸・京谷史子・吉田健吾・村中厚哉
  • Organizer: 第３回CSJ化学フェスタ２０１３
  • Place of Presentation: タワーホール船堀（東京）
• [Presentation] Design and Synthesis of Near-infrared Absorbing Phthlocyanine Analogues (2013)
  • Author(s): A. Muranaka, M. Uchiyama
  • Organizer: The First SJTU-RIKEN Workshop on Energy and Environment
  • Place of Presentation: Shanghai Jiao Tong University (China)
  • Invited
• [Presentation] Design, Synthesis, and Electronic Properties of Near-infrared Absorbing Phthalocyanine Analogues (2012)
  • Author(s): Muranaka, A., et al.
  • Organizer: The 7th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-7)
  • Place of Presentation: Nanyang Technological University, Singgpore(招待講演)
  • Year and Date: 2012-12-12
• [Presentation] 芳香族性ヘミポルフィラジンの合成と電子構造解析 (2012)
  • Author(s): 村中厚哉, 他
  • Organizer: 第23回基礎有機化学討論会
  • Place of Presentation: 京都テルサ(京都市)
  • Year and Date: 2012-09-20
• [Presentation] Synthesis and Electronic Properties of[18]/[20]πHemiporphyrazines (2012)
  • Author(s): Muranaka, A., et al.
  • Organizer: 7th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Jeju, Korea(招待講演)
  • Year and Date: 2012-07-02