<i>D</i>_3<i>h</i>‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

• 大古田, 燿平

• 浅石, 茜

• 並木, 智哉

• 橋本, 朋昭

• 山田, 翠

• 白井, 公一郎

• 片上, 勇太

• 菅谷, 知明

• 田所, 誠

• 佐竹, 彰治

書誌事項

タイトル別名

• D3h -Symmetric Porphyrin-Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One-Nanometer-Sized Cavity.

抄録

The one-step synthesis of D3h -symmetric cyclic porphyrin trimers 1 composed of three 2,2'-[4,4'-bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel-mediated reductive coupling of meso-5,15-bis(6-chloro-4-methoxycarbonylpyrid-2-yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X-ray crystallography. Treatment of an η(3) -allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η(3) -allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.

The one-step synthesis of D3h -symmetric cyclic porphyrin trimers 1 composed of three 2,2'-[4,4'-bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel-mediated reductive coupling of meso-5,15-bis(6-chloro-4-methoxycarbonylpyrid-2-yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X-ray crystallography. Treatment of an η(3) -allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η(3) -allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.

収録刊行物

• Chemistry - A European Journal

  Chemistry - A European Journal 21 (33), 11745-11756, 2015-08-10

  Wiley

キーワード

• column chromatography
• macrocycles
• multinuclear complex
• porphyrinoids
• synthesis design

詳細情報

• CRID: 1050001338905074432
• NII論文ID: 120006768426
• DOI: 10.1002/chem.201501854
• ISSN: 15213765
• ISSN: 09476539
• Web Site: https://tus.repo.nii.ac.jp/records/2483
• Web Site: https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.201501854
• Web Site: http://onlinelibrary.wiley.com/wol1/doi/10.1002/chem.201501854/fullpdf
• 本文言語コード: en
• 資料種別: journal article
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