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ヘキサデカピリン- ((1.0.0.1.1.0.1.0.0.1.1.0.1)):熱的形状の変化をサポートする二重サイトリガンド
Gonzalo Anguera1, Won-Young Cha2, Matthew D Moore1
1Department of Chemistry , The University of Texas at Austin , 105 East 24th Street, Stop A5300 , Austin , Texas 78712-1224 , United States.
Journal of the American Chemical Society
|February 23, 2018
まとめ
新しいヘクサデカフィリンマクロサイクルが合成され,二金属亜鉛とコバルト複合体を形成した. これらの複合体は異なる形状を示し,熱センサーとして使用する可能性を示しています.
科学分野:
- 超分子化学
- 有機合成
- 材料科学
背景:
- 拡張されたポルフィーリンは,ユニークな電子および構造的性質を持つマクロサイクル化合物です.
- バイメタリック複合体は,複数の金属中心の相互作用により,新しい機能の機会を提供します.
- マクロサイクルにおけるコンフォーマーションの柔軟性は,調節可能な特性につながる.
研究 の 目的:
- 新しい拡張ポルフィリンであるヘクサデカピリンを合成する.
- 合成されたヘクサデカピリンで二金属亜鉛とコバルト複合体の形成と特徴を調査する.
- これらの複合体のコンフォメーション行動と電子特性を潜在的応用のために探求する.
主な方法:
- ヘクサピロール誘導体とクアターピロール前駆体との凝縮反応.
- 亜鉛,コバルト,および混合亜鉛/コバルト双金属複合物の形成と特徴付け
- 顕微鏡分析 (NMR,UV-Vis,質量スペクトロメトリー) と単結晶X線微分.
- 密度関数理論 (DFT) 計算と一時的吸収スペクトロスコーピー.
主要な成果:
- 8つの直接的なα-ピロル-α-ピロル結合によるヘクサデカフィリンマクロサイクルの合成に成功した.
- 安定した二金属亜鉛とコバルト複合体の形成
- 同じ酸化状態のコバルト二金属複合体の2つの安定した相互変換形状の識別.
- 構造と電子の詳細な特徴,形状効果に関するDFTの洞察を含む.
結論:
- 新しいヘクサデカフィリンは複雑な二金属系を構成する多機能リガンドとして機能する.
- 金属複合体の構成動態は重要であり,それらの電子特性に影響を与えます.
- このマクロサイクルシステムは 蓄積された熱のセンサーとしての可能性を 示しています
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