2002 Fiscal Year Annual Research Report

多重N―混乱ポルフィリンの合成および機能集積化

Research Project

Project/Area Number	13440189
Research Institution	Kyushu University
Principal Investigator	古田弘幸九州大学, 工学研究院, 教授 (40244157)
Keywords	ポルフィリン / N-混乱ポルフィリン / ポルフィリン異性体 / 金属錯体 / カリックスフィリン / 拡張ポルフィリン / ヘキサフィリン / 芳香族性
Research Abstract	多重N-混乱ポルフィリンの合成戦略を検討するために、まず、想定しうる95個の構造異性体(互変異性体を含む)すべてについて、密度汎関法を用いて、安定構造、エネルギー、芳香族指標の計算を行った。その結果、ピロール環が一個反転するごとに、約18Kcal/molの不安定化がおこることが判明した。実際に二重混乱体の合成を試みたところ、目的化合物の一方であるシス体と、コロリンやオキシインドロフィリンといった新規ポルフィリノイドが生成すること、またシス体の金属錯体が特異な電気化学挙動や、光反応性を示すこと、さらには銅錯化の際、分解されてトリピリノンに変換されることなどを明らかにした。一方、環拡張系混乱ポルフィリノイドの展開として、サフィリンからノナフィリンまでの拡張ポルフィリンの構造決定を行い、平面性と環状構造とは直接関係しないことを明確に示した。しかしながら、混乱ピロールユニットを2個導入したヘキサフィリンでは平面構造をとり、2つの金属イオンを内部に取り込む芳香族性ポルフィリノイドであること、X線構造解析より明らかにした。金属配位様式としては、外周部窒素が配位に関与して対面型二量体を形成する性質があることを、亜鉛錯体により、明らかにした。さらに、共役系を持たない、カリックスフィリン系での混乱ポルフィリンでは、弱い炭素-金属相互作用が存在することを、亜鉛やカドニウムの錯体を合成して明らかにした。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] Araki, K.: "Acid-Base and Spectroelectrochemical Properties of Doubly N-Confused Porphyrins"Inorg. Chem.. 40. 2020-2025 (2001)
[Publications] Pushpan, S.K.: "N-Confused Expanded Porphyrins : First Example of a Modified Sapphyrin with an Inverted N-Confused Pyrrole Ring"J. Am. Chem. Soc.. 123. 5138-5139 (2001)
[Publications] Furuta, H.: "Metal Complexes of N-Confused Calix[4]phyrin Derivative-The First X-ray Structure of Organometallic Compound of Divalent Copper"Angew. Chem. Int. Ed.. 40. 2323-2325 (2001)
[Publications] Furuta, H.: "NH Tautomerism of N-Confused porphyrin"J. Am. Chem. Soc.. 123. 6207-6208 (2001)
[Publications] Furuta, H.: "Oxyindolophyrin : A Novel Fluoride Receptor Derived from N-Confused Corrole Isomer"J. Am. Chem. Soc.. 123. 6435-6436 (2001)
[Publications] Shin, J.-Y: "Meso-Aryl Substituted Expanded Porphyrins"J. Am. Chem. Soc.. 123. 7190-7191 (2001)
[Publications] Furuta, H.: "Theoretical Study of Stability, Structures, and Aromaticity of Multiply N-Confused Porphyrins"J. Org. Chem.. 66. 8563-8572 (2001)
[Publications] Alagar, S.: "The First bis-Rh(I) Complex of N-Confused Porphyrin"Chem. Commun.. 1666-1667 (2001)
[Publications] Furuta, H.: "Regioselective Oxidative Liberation of Aryl-Substituted Tripyrrinone Metal Complexes from N-Confused Porphyrin"Org. Lett.. 4. 181-184 (2002)
[Publications] Furuta, H.: "Flexible Inner and Outer Coordination of Zn(II) N-Confused Porphyrin Complex"J. Am. Chem. Soc.. 124. 5622-5623 (2002)
[Publications] Furuta, H.: "Confusion, Inversion, and Creation -A New Spring from Porphyrin Chemistry"Chem. Commun.. 1795-1804 (2002)
[Publications] Shinmori, H: "Effective Face-to-face Dimerization of A Crown Ether Appended N-Confused porphyrins"Tetrahedron Lett.. 43. 4881-4884 (2002)
[Publications] Shimizu, S.: "Perfluorinated meso-Aryl Expanded Porphyrins"Angew. Chem. Int. Ed.. 42. 78-82 (2003)
[Publications] Furuta, H.: "Crystal Structures of Palladium(II) and Copper(II) Complexes of meso-Phenyl Tripyrrinone"Inorg. Chem. Commun.. 6. 162-164 (2003)
[Publications] Furuta, H.: "Zinc Complex of N-confused Calix[4]phyrin"Inorg. Chem. Commun.. 6. 398-401 (2003)
[Publications] Furuta, H.: "Chemistry of N-confused Porphyrin : A Novel Porphyrin Isomer"J. Oleo. Sci.. 3. 878-879 (2003)
[Publications] Alagar, S.: "Doubly N-Confused Hexaphyrin : A Novel Aromatic Expanded Porphyrin that Complexes Bis-Metals in the Core"J. Am. Chem. Soc.. 125. 878-879 (2003)
[Publications] Araki, K.: "Doubly N-Confused Porphyrins as Efficient Sensitizers for Singlet Oxygen Generation"Chem. Lett.. 32. 244-245 (2003)
[Publications] Taniguchi, R.: "Ring Size Selective Synthesis of meso-Aryl Expanded Porphyrins"Tetrahedron Lett.. 44. 2505-2507 (2003)
[Publications] Furuta, H.: "Facile Formation of N-Confused Porphyrin Dimers by Pt(II) Coordination to Outer-Nitrogens"Angew. Chem. Int. Ed.. 42(印刷中). (2003)
[Publications] Maeda, H.: "N-Confused Porphyrin Bearing meso-Perfluorophenyl Groups : A Potential Agent that Forms Stable Squareplanar Complexes with Cu(II) and Ag(III)"Org. Lett.. 5(印刷中). (2003)

2002 Fiscal Year Annual Research Report

多重N―混乱ポルフィリンの合成および機能集積化

Principal Investigator

古田 弘幸 九州大学, 工学研究院, 教授 (40244157)

Research Products

[Publications] Araki, K.: "Acid-Base and Spectroelectrochemical Properties of Doubly N-Confused Porphyrins"Inorg. Chem.. 40. 2020-2025 (2001)

[Publications] Pushpan, S.K.: "N-Confused Expanded Porphyrins : First Example of a Modified Sapphyrin with an Inverted N-Confused Pyrrole Ring"J. Am. Chem. Soc.. 123. 5138-5139 (2001)

[Publications] Furuta, H.: "Metal Complexes of N-Confused Calix[4]phyrin Derivative-The First X-ray Structure of Organometallic Compound of Divalent Copper"Angew. Chem. Int. Ed.. 40. 2323-2325 (2001)

[Publications] Furuta, H.: "NH Tautomerism of N-Confused porphyrin"J. Am. Chem. Soc.. 123. 6207-6208 (2001)

[Publications] Furuta, H.: "Oxyindolophyrin : A Novel Fluoride Receptor Derived from N-Confused Corrole Isomer"J. Am. Chem. Soc.. 123. 6435-6436 (2001)

[Publications] Shin, J.-Y: "Meso-Aryl Substituted Expanded Porphyrins"J. Am. Chem. Soc.. 123. 7190-7191 (2001)

[Publications] Furuta, H.: "Theoretical Study of Stability, Structures, and Aromaticity of Multiply N-Confused Porphyrins"J. Org. Chem.. 66. 8563-8572 (2001)

[Publications] Alagar, S.: "The First bis-Rh(I) Complex of N-Confused Porphyrin"Chem. Commun.. 1666-1667 (2001)

[Publications] Furuta, H.: "Regioselective Oxidative Liberation of Aryl-Substituted Tripyrrinone Metal Complexes from N-Confused Porphyrin"Org. Lett.. 4. 181-184 (2002)

[Publications] Furuta, H.: "Flexible Inner and Outer Coordination of Zn(II) N-Confused Porphyrin Complex"J. Am. Chem. Soc.. 124. 5622-5623 (2002)

[Publications] Furuta, H.: "Confusion, Inversion, and Creation -A New Spring from Porphyrin Chemistry"Chem. Commun.. 1795-1804 (2002)

[Publications] Shinmori, H: "Effective Face-to-face Dimerization of A Crown Ether Appended N-Confused porphyrins"Tetrahedron Lett.. 43. 4881-4884 (2002)

[Publications] Shimizu, S.: "Perfluorinated meso-Aryl Expanded Porphyrins"Angew. Chem. Int. Ed.. 42. 78-82 (2003)

[Publications] Furuta, H.: "Crystal Structures of Palladium(II) and Copper(II) Complexes of meso-Phenyl Tripyrrinone"Inorg. Chem. Commun.. 6. 162-164 (2003)

[Publications] Furuta, H.: "Zinc Complex of N-confused Calix[4]phyrin"Inorg. Chem. Commun.. 6. 398-401 (2003)

[Publications] Furuta, H.: "Chemistry of N-confused Porphyrin : A Novel Porphyrin Isomer"J. Oleo. Sci.. 3. 878-879 (2003)

[Publications] Alagar, S.: "Doubly N-Confused Hexaphyrin : A Novel Aromatic Expanded Porphyrin that Complexes Bis-Metals in the Core"J. Am. Chem. Soc.. 125. 878-879 (2003)

[Publications] Araki, K.: "Doubly N-Confused Porphyrins as Efficient Sensitizers for Singlet Oxygen Generation"Chem. Lett.. 32. 244-245 (2003)

[Publications] Taniguchi, R.: "Ring Size Selective Synthesis of meso-Aryl Expanded Porphyrins"Tetrahedron Lett.. 44. 2505-2507 (2003)

[Publications] Furuta, H.: "Facile Formation of N-Confused Porphyrin Dimers by Pt(II) Coordination to Outer-Nitrogens"Angew. Chem. Int. Ed.. 42(印刷中). (2003)

[Publications] Maeda, H.: "N-Confused Porphyrin Bearing meso-Perfluorophenyl Groups : A Potential Agent that Forms Stable Squareplanar Complexes with Cu(II) and Ag(III)"Org. Lett.. 5(印刷中). (2003)

古田弘幸九州大学, 工学研究院, 教授 (40244157)