感応性近赤外センサーを目指したリンを含むフタロシアニン類縁体の創出

• Project Area: Stimuli-responsive Chemical Species for the Creation of Functional Molecules
• Project/Area Number: 25109502
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tohoku University
• Principal Investigator: 小林 長夫 東北大学, 理学(系)研究科(研究院), 教授 (60124575)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000); Fiscal Year 2014: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2013: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
• Keywords: 感応 / フタロシアニン / コロール / テトラアザポルフィリン / 吸収 / 合成 / 近赤外機能色素 / 典型元素化学 / 化学応答分子

Outline of Annual Research Achievements

外部応答（光、酸、塩基、参加還元）に鋭敏に応答する感応性燐フタロシアニン(Pc)及び類縁体の開発・機能解明が目的であった。主な成果を以下に記述する。1)燐テトラアザポルフィリンの周辺にaryl基を導入してスペクトルを調べた。これらの化合物は可視部に強い電荷移動吸収帯を示すが、aryl基上の電子吸引性・供与性によりその強度と位置が大きく変わり、可視部全体で光を吸収した。2)燐テトラベンゾコロールは２つのOH基を軸配位子として持つが、溶解する溶媒を塩基性にする事により軸配位子は酸素一つに成り、吸収が大きく変化した。3)無金属体に比べ燐テトラベンゾコロールの酸素架橋2量体は一重項酸素生成効率が高く増感材として有望である。3)燐テトラベンゾコロールの軸配位子を用いサブフタロシアニンを2個酸素架橋にて結合すると、可視部の幅広い領域で吸収を示すが、それはモノマーのスペクトルの重ね合わせでなく、相互作用により幅広となったため、可視部の光を有効に捕集する事が出来る。4)燐5価Pcの平面は燐のイオン半径が小さいため大きくひずんでいるが、置換基を変化させその歪みの程度を変えても吸収位置は殆ど変化しない事が判明した。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Synthesis and Optical Properties of Tetraazaporphyrin Phosphorus(V) Complexes with Electron-Rich Heteroatoms (2015)
  • Author(s): Yoshida, T.; Furuyama, T.; Kobayashi, N.
  • Journal Title: Tetrahedron Lett. Volume: 56 Issue: 13 Pages: 1671-1674
  • DOI: 10.1016/j.tetlet.2015.02.033
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Structural Changes in Non-Planar Octaaryl Substituted Phthalocyanine Phosphorus Complexes (2015)
  • Author(s): Furuyama, T.; Harako, R.; Kobayashi, N.
  • Journal Title: J. Porphyrin Phthalocyanines Volume: 19 Issue: 01-03 Pages: 500-509
  • DOI: 10.1142/s1088424615500364
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Phosphorous(V) Corrole: Synthesis, Spectroscopic Properties, Theoretical Calculations and Potential Utility for In Vivo Applications in Living Cells (2014)
  • Author(s): X. Liang, J. Mack, L. -M. Zheng, Z. Shen, and N. Kobayashi
  • Journal Title: Inorg. Chem. Volume: 53 Issue: 6 Pages: 2797-2802
  • DOI: 10.1021/ic402347w
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Phosphorus(V) Tetraazaporphyrins: Porphyrinoids Showing an Exceptionally Strong CT Band between the Soret and Q Bands (2014)
  • Author(s): Furuyama, T.; Yoshida, T.; Hashizume, D.; Kobayashi, N.
  • Journal Title: Chem. Sci. Volume: 5 Issue: 6 Pages: 2466-2474
  • DOI: 10.1039/c4sc00569d
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis of Tetrabenzotriazacorrole μ-oxo Dimer and Investigation of Its Stacking Effect (2014)
  • Author(s): T. Furuyama, Y. Sugiya, and N. Kobayashi
  • Journal Title: Chem. Commun. Volume: 50 Pages: 4312-4314
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis of Tetrabenzotriazacorrole-Subphthalocyanine μ-Oxo Triad (2014)
  • Author(s): Furuyama, T.; Sugiya, Y.; Kobayashi, N.
  • Journal Title: Macroheterocycles Volume: 7 Issue: 2 Pages: 139-144
  • DOI: 10.6060/mhc140488k
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Reduction-Triggered Aromatic to Aromatic Electronic Structure Switching in a Tribenzotetraazachlorin-Fullerene Conjugate (2014)
  • Author(s): T. Fukuda, J. Sato, N. Hashimoto, and N. Kobayashi
  • Journal Title: Chem. Commun. Volume: 50 Issue: 91 Pages: 14269-14272
  • DOI: 10.1039/c4cc04689g
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Control of Absorption Properties of Tetraazaporphyrin Group 15 Complexes by Modification of their Axial Ligands (2014)
  • Author(s): Furuyama, T.; Asai, M.; Kobayashi, N.
  • Journal Title: Chem. Commun. Volume: 50 Issue: 95 Pages: 15101-15104
  • DOI: 10.1039/c4cc07408d
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Acenaphthylene-fused cyclo[8]pyrroles with intense NIR region absorption bands (2013)
  • Author(s): T. Okujima, C. Ando, J. Mack, S. Mori, I. Hisaki, T. Nakae, H. Yamada, K. Ohara, N. Kobayashi, H. Uno
  • Journal Title: Chemistry - A European Journal Volume: vol.19 (41) Issue: 41 Pages: 13970-13978
  • DOI: 10.1002/chem.201301294
  • Peer Reviewed
• [Journal Article] Magnetic Circular Dichroism Spectroscopy and Electronic Structures of C3 Symmetry Buckybowls (2013)
  • Author(s): J. Mack, Y. Morita, S. Higashibayashi, H. Sakurai, and N. Kobayashi
  • Journal Title: Chem. Phys. Lett. Volume: 556 Pages: 188-194
  • Peer Reviewed
• [Journal Article] High-Performance Aqueous Asymmetric Electrochemical Capacitors based on Graphene Oxide/Cobalt(II)-Tetrapyrazinoporphyrazine Hybrids (2013)
  • Author(s): J. N. Lekitima, K. I. Ozoemena, C. J. Jafta, N. Kobayashi, Y. Song, D. Tong, S. Chen, and M. Oyama
  • Journal Title: J. Mater. Chem. A Volume: 1 Issue: 8 Pages: 2821-2826
  • DOI: 10.1039/c2ta01325h
  • Peer Reviewed
• [Journal Article] Highly Deformed Phthalocyanine as a Suitable Scafold for Pristine Fullerenes (2013)
  • Author(s): S. Shimizu, A. Miura, and N. Kobayashi
  • Journal Title: CrystEngComm. Volume: 15 Issue: 19 Pages: 3759-3762
  • DOI: 10.1039/c2ce26618k
  • Peer Reviewed
• [Journal Article] Pyrrolopyrrole aza-BODIPY analogues: a facile synthesis and intense fluorescence (2013)
  • Author(s): Soji Shimizu, Taku Iino, Yasuyuki Araki, and Nagao Kobayashi
  • Journal Title: Chemical Communication Volume: 49 Issue: 16 Pages: 1621-1623
  • DOI: 10.1039/c3cc38452g
  • Peer Reviewed
• [Journal Article] Application of MCD Spectroscopy and TD-DFT to Endohedral Metallofullerenes for Characterization of Their Electronic Transitions (2013)
  • Author(s): Yamada, M.; Slanina, Z.; Mizorogi, N.; Muranaka, A.; Maeda, Y.; Nagase, S.; Akasaka, T.; Kobayashi, N.
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 15 Issue: 10 Pages: 3593-3601
  • DOI: 10.1039/c3cp44096f
  • Peer Reviewed
• [Journal Article] Absorption and Electrochemical Properties of Cobalt and Iron Phthalocyanines and Their Quaternized Derivatives: Aggregation Equilibrium and Oxygen Reduction Electrocatalysis (2013)
  • Author(s): Tasso, T. T.; Furuyama, T.; Kobayashi, N.
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 16 Pages: 9206-9215
  • DOI: 10.1021/ic4002048
  • Peer Reviewed
• [Journal Article] A μ-Oxo Hetero Dimer of Silicon Phthalocyanine and Naphthalocyanine (2013)
  • Author(s): K. Oniwa, S. Shimizu, T. Fukuda, N. Kobayashi
  • Journal Title: Chem. Commun Volume: Vol. 49 Issue: 75 Pages: 8341-8343
  • DOI: 10.1039/c3cc44490b
  • Peer Reviewed
• [Journal Article] MCD Spectroscopy and TD-DFT Calculations of a Naphthalene-ring-bridged Coplanar Binuclear Phthalocyanine Dimer (2013)
  • Author(s): J. Mack, X. Liang, T. V. Dubinina, L. G. Tomilorva, T. Nyokong, and N. Kobayashi
  • Journal Title: J. Porphyrins and Phthalocyanines Volume: 17 Issue: 06n07 Pages: 489-500
  • DOI: 10.1142/s1088424613500259
  • Peer Reviewed
• [Journal Article] Synthesis and Properties of Non-Planar Octaphenyl-Substituted Phthalocyaninato Manganese(III) (2013)
  • Author(s): T. Fukuda, K. Yamamoto, and N. Kobayashi
  • Journal Title: J. Porphyrins and Phthalocyanines Volume: 17 Pages: 756-762
  • Peer Reviewed
• [Journal Article] Inversion of the stereochemistry around the Sulfur Atom of the Axial Methiopnine Side Chain through Alternation of Amino Acid Side Chain Packing in Hydrogenobacter thermophiles Cytochrome c552 and Its Functional Consequences (2013)
  • Author(s): H. Tai, K. Tonagawa, T. Shibata, H. Hemmi, N. Kobayashi, and Y. Yamamoto
  • Journal Title: Biochemistry Volume: 52 Pages: 4800-4809
  • Peer Reviewed
• [Journal Article] MCD Spectroscopy and TD-DFT Calculations of Low-Symmetry Acenaphthoporphyrins with Dual Fluorescence (2013)
  • Author(s): J. Mack, J. Nakamura, T. Okujima, H. Yamada, H. Uno, and N. Kobayashi
  • Journal Title: J. Porphyrins and Phthalocyanines Volume: 17 Pages: 996-1007
  • Peer Reviewed
• [Journal Article] Fluorescence Detected Induced Circular Dichroism Observed for Optically Active Binaphthyl-Linked Metal-Free and Zinc Phthalocyanines (2013)
  • Author(s): N. Kobayashi
  • Journal Title: Macroheterocycles Volume: 6 Issue: 2 Pages: 134-136
  • DOI: 10.6060/mhc130538k
  • Peer Reviewed
• [Journal Article] Nickel and palladium complexes of seco-tribenzoporphyrazines derived from one-pot condensation of 1,3-diiminoisoindoline (2013)
  • Author(s): Ippei Sugita, Soji Shimizu, Takamitsu Fukuda, and Nagao Kobayashi
  • Journal Title: Tetrahedron Letters Volume: 54 Issue: 12 Pages: 1599-1601
  • DOI: 10.1016/j.tetlet.2013.01.057
  • Peer Reviewed
• [Journal Article] Electrochemical Capacitors Based on Nitrogen-enriched Cobalt(II) Phthaloycanine/Multi-walled Carbon Nanotube Nanocomposites (2013)
  • Author(s): J. N. Lekitima, K. I. Ozoemena, N. Kobayashi
  • Journal Title: ECS Transactions Volume: 50 Issue: 43 Pages: 125-132
  • DOI: 10.1149/05043.0125ecst
  • Peer Reviewed
• [Presentation] Development of Azaporphyrin Complexes with Main-Group Elements (2014)
  • Author(s): T. Furuyama and N. Kobayashi
  • Organizer: Michinoku International Symposium on Porphyrins, Phthalocyanines and Functional π Molecules
  • Place of Presentation: Zao, Miyagi, Japan
  • Year and Date: 2014-10-13 – 2014-10-16
• [Presentation] Phosphorus(V) Tetraazaporphyrins; Their Unique Optical Properties and Substituents Effects (2014)
  • Author(s): T.Yoshida, T. Furuyama, and N. Kobayashi
  • Organizer: Michinoku International Symposium on Porphyrins, Phthalocyanines and Functional π Molecules
  • Place of Presentation: Zao, Miyagi, Japan
  • Year and Date: 2014-10-13 – 2014-10-16
• [Presentation] Synthesis of Highly Deformed α-Octaaryl Phthalocyanine Phosphorous(V) Complexes (2014)
  • Author(s): R. Harako, T. Furuyama, and N. Kobayashi
  • Organizer: The 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul, Turkey
  • Year and Date: 2014-06-22 – 2014-06-27
• [Presentation] Synthesis and Characterization of Tetrabenzotriazacorrole and Its π-Oxo Dimer (2014)
  • Author(s): Y. Sugiya, T. Furuyama, and N. Kobayashi
  • Organizer: The 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul, Turkey
  • Year and Date: 2014-06-22 – 2014-06-27
• [Presentation] Phosphorous(V) Tetraazaporphyrins Showing an Intense CT Band Comperative to the Soret and Q Bands (2014)
  • Author(s): T. Yoshida, T. Furuyama, and N. Kobayashi
  • Organizer: The 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul, Turkey
  • Year and Date: 2014-06-22 – 2014-06-27
• [Presentation] Design, Synthesis, and Properties of Near-IR-Absorbing Phthalocyanine Complexes with Main-Group Elements (2014)
  • Author(s): T. Furuyama, K. Satoh, T. Kushiya, N. Kobayashi
  • Organizer: The 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul, Turkey
  • Year and Date: 2014-06-22 – 2014-06-27
• [Presentation] 置換基効果に着目したテトラアザポルフィリン五価リン錯体の合成と物性 (2014)
  • Author(s): 吉田拓矢、古山渓行、小林長夫
  • Organizer: 第94回日本化学会春季年会
  • Place of Presentation: 名古屋
• [Presentation] ピロロピロールで連結されたアザジピロメテン類縁体の金属錯体の合成および物性 (2014)
  • Author(s): 高橋友一、清水宗治、小林長夫
  • Organizer: 第94回日本化学会春季年会
  • Place of Presentation: 名古屋
• [Presentation] Drastic Change in Optical Properties of Tetraazaporphyrins Caused by Phosphorus(V) Insertion (2013)
  • Author(s): T. Yoshida, T. Furuyama, N. Kobayashi
  • Organizer: 15th International Symposium on Novel Aromatic Compounds (ISNA-15)
  • Place of Presentation: 台北(台湾）
• [Presentation] リン錯化によるアザポルフィリンの特異な吸収特性変化とその制御 (2013)
  • Author(s): 吉田拓矢、古山渓行、小林長夫
  • Organizer: 第40回有機典型元素化学討論会
  • Place of Presentation: 東大阪
• [Presentation] 感応性近赤外センサーを目指したリンを含むフタロシアニン類縁体の創出 (2013)
  • Author(s): 小林長夫
  • Organizer: 感応性化学種が拓く新物質科学 第2回公開シンポジウム
  • Place of Presentation: 福岡
• [Presentation] Relationship between the Molecular Structures and Spectroscopic and Electrochemical Properties of Porphyrinoids (2013)
  • Author(s): N. Kobayashi
  • Organizer: Modern Methods in Theoretical and Experimental Electrochemistry
  • Place of Presentation: Plios, Ivanovo region, Russia
  • Invited
• [Book] 高次π空間の創発と機能開発 (2013)
  • Author(s): 清水宗治、小林長夫
  • Total Pages: 245
  • Publisher: シーエムシー
• [Book] 機能性色素の化学 (2013)
  • Author(s): 小林長夫
  • Total Pages: 353
  • Publisher: 化学同人
• [Remarks] 東北大学大学院理学研究科化学専攻 機能分子化学研究室
  • URL: http://kinou.chem.tohoku.ac.jp/KobayashiLabHP/Home.html
• [Remarks] Functional Molecular Chemistry Lab.
  • URL: http://kinou.chem.tohoku.ac.jp/KobayashiLabHP/Home_English.html