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Bisbidentate型架橋配位子を用いた集積型金属錯体の合成と構造 -自然分晶する不斉環状亜鉛四核錯体
https://ir.soken.ac.jp/records/312
https://ir.soken.ac.jp/records/31288850dc0-ccd6-47c9-863e-31b6ec611c92
| 名前 / ファイル | ライセンス | アクション |
|---|---|---|
要旨・審査要旨 / Abstract, Screening Result (246.0 kB)
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本文 / Thesis (2.3 MB)
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| Item type | 学位論文 / Thesis or Dissertation(1) | |||||||
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| 公開日 | 2010-02-22 | |||||||
| タイトル | ||||||||
| タイトル | Bisbidentate型架橋配位子を用いた集積型金属錯体の合成と構造 -自然分晶する不斉環状亜鉛四核錯体 | |||||||
| 言語 | ||||||||
| 言語 | jpn | |||||||
| 資源タイプ | ||||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_46ec | |||||||
| 資源タイプ | thesis | |||||||
| 著者名 |
森下, 泰全
× 森下, 泰全
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| フリガナ |
モリシタ, ヒロマサ
× モリシタ, ヒロマサ
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| 著者 |
MORISHITA, Hiromasa
× MORISHITA, Hiromasa
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| 学位授与機関 | ||||||||
| 学位授与機関名 | 総合研究大学院大学 | |||||||
| 学位名 | ||||||||
| 学位名 | 博士（理学） | |||||||
| 学位記番号 | ||||||||
| 内容記述タイプ | Other | |||||||
| 内容記述 | 総研大甲第489号 | |||||||
| 研究科 | ||||||||
| 値 | 数物科学研究科 | |||||||
| 専攻 | ||||||||
| 値 | 08 機能分子科学専攻 | |||||||
| 学位授与年月日 | ||||||||
| 学位授与年月日 | 2000-09-29 | |||||||
| 学位授与年度 | ||||||||
| 値 | 2000 | |||||||
| 要旨 | ||||||||
| 内容記述タイプ | Other | |||||||
| 内容記述 | The metal-assisted assembly of cyclic molecular arrays plays an integral part in the development of inclusion chemistry as well as "engineering up" molecular architectures. The creation of a new class of artificial chiral supramolecular species via spontaneous self-assembly has been one key to further development of this rapidly expanding field. However, only a few examples of chiral molecular squares have been reported. In particular, synthetic approach using achiral ligands is very rare. They describe a one-pot, high-yield synthesis of a novel cyclic tetranuclear ZnII complex (3-1) with 3, 6-di-2-pyridyl-1, 2, 4, 5-tetrazine (DPTZ), which was spontaneously resolved as chiral crystals (scheme 1). The X-ray crystal structure and the solution behaviors of this complex (2-1) have been investigated in this work. Interestingly, the individual single crystal was found to consist of one enantiomer only. This is the first example of a quantitative formation of a spontaneously resolved cyclic product based on self assembly of metal ions and achiral ligands. In addition, it is noteworthy that this is the first example of the chiral cyclic tetranuclear species that was constructed by kinetically labile ZnII complexes. These results will provide a new tool for creating chiral supramolecular architectures using inherently chiral metal ions and achiral ligands. Solvent effect on the structure of complex (2-1) and optical resolution of (2-1) were investigated using NMR, mass, and circular dichroism spectrometries. They found that the ligand DPTZ itself reacted with CuII and PbII ions, probably because these metals are stronger Lewis acids than ZnII ions. Then they synthesized a more robust ligand, 2, 5-di-2-pyridyl-pyrazine (DPPZ), which was expected to form more stable metal complexes. They have prepared two types of one-dimensional polymers AgI polymer complexes with DPPZ. The kind of counter anions dramatically affected their polymeric structures. When perchlorate anions are used as the counter anion (3-5), AgI ions were aligned in the zig-zag manner (Fig 1), whereas AgI ions were aligned linearly when nitrate ions were used (Fig 2). Further, in the former case, the coordination geometry of AgI is distorted square planar, while the latter complex is in the distorted octahedral geometry. The fine structures and chemical properties of these complexes will be reported. The X-ray analysis of the ZnII complex of DPPZ is now underway to compare with that of DPTZ. |
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| 所蔵 | ||||||||
| 値 | 有 | |||||||
| フォーマット | ||||||||
| 内容記述タイプ | Other | |||||||
| 内容記述 | application/pdf | |||||||
| 著者版フラグ | ||||||||
| 出版タイプ | AM | |||||||
| 出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||||
