レドックス反応性H結合:陽子結合電子移転を使用して電子移転の効果を拡大する
Hyejeong Choi1, Kiyeol Baek1, Sean T Toenjes1
1Department of Chemistry and Biochemistry, San Diego State University, San Diego, California 92182-1030, United States.
Journal of the American Chemical Society
|September 28, 2020
まとめ
新しい戦略では,陽子結合電子の移転により,酸化還元反応性水素結合ダイマーが作られます. この方法は,電子誘導による陽子の移転によって結合強度を大幅に高め,より強いイオン水素結合につながります.
科学分野:
- 超分子化学
- 電気化学
- 有機化学
背景:
- 水素結合 (H結合) ダイマーは分子認識において極めて重要です.
- 二次 H 結合は,H 結合ダイマーの全体的な結合強度に大きな影響を与える.
- 外部刺激によってH結合二元体の安定性を制御することは重要な課題です.
研究 の 目的:
- 高酸化還元反応性Hボンドジマーを作るための新しい戦略を提案し,実証する.
- 陽子結合電子移転 (PCET) を利用して,H結合二極体安定性を調節する.
- PCETによる結合強化における二次H結合の役割を調査する.
主な方法:
- 電動ドナー-受容器-ドナー (DAD) 配列 (H(MQ+) と電動不活性受容器-受容器 (ADA) 配列 (O(NH) の設計と合成
- 初期結合定数 (Kassoc) を決定するための核磁共振 (NMR) 定位.
- 循環式電圧測定 (CV) で,還元作用と還元時の結合変化を研究する.
主要な成果:
- H ((MQ+) H:O ((NH) Oダイマーは,酸化状態で典型的な500M−1のカソックを示した.
- システムの2電子の減少は結合強度の1.8×105倍増加をもたらした.
- 還元された状態は,強いDDD-AAA H結合ダイマーの特徴である9 × 107 M-1のKassocを示し,陽子の移転を示した.
結論:
- 提案されたPCET戦略は,高酸化還元反応性H結合二極体を生成する.
- 電子の移動は陽子の移動を誘発し,H結合の相互作用を大幅に強化します.
- このアプローチは 切り替え可能な分子認識システムの設計に 有力な方法を提供します
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