フォトクロミック[Pd2ディチエニレタン4]の光スイッチングとゲスト結合のメカニズム的な相互作用
Ru-Jin Li1, Julian J Holstein1, Wolf G Hiller1
1Faculty of Chemistry and Chemical Biology , TU Dortmund University , Otto-Hahn-Straße 6 , 44227 Dortmund , Germany.
Journal of the American Chemical Society
|January 9, 2019
まとめ
ディチエニレタン (DTE) リガンドを使用した光色調整ケージは,光照射でゲストを解放することができます. この研究では 光スイッチを"つ閉めると チンパンジーが外に出るので 檻の仕組みについて 新たな洞察が得られます
科学分野:
- 超分子化学
- 写真化学
- 材料科学
背景:
- 光色調整ケージは,光制御されたゲストエンカプセルとリリースを提供します.
- 以前の研究では,完全にスイッチされた状態に焦点を当て,中間の光異性化メカニズムが不明でした.
研究 の 目的:
- ディチエニレチン (DTE) ベースの調整ケージでの光異性化過程におけるゲストの排出のメカニズム的詳細を調査する.
- フォトイソメリゼーションのステップとケージ腔内のゲストの位置の相互作用を理解する.
主な方法:
- 固有のキラリティを持つ新しいDTEベースの光色調整ケージの合成.
- ホスト-ゲスト複合は,キラル1R-(−) -または1S-(+) - カンフォール硫酸塩 (CSA) による.
- 円形二重化 (CD),DOSY NMR,イオン移動質量スペクトロメトリー,X線結晶学を用いた光同化とキラリティの移転のモニタリング.
主要な成果:
- ゲスト (CSA) から宿主ケージへのキラリティの移転は,CDスペクトロスコーピーを用いて観察された.
- 放射線は安定した"閉じた"光同位体を生じさせ,高いエナティオメア過剰でキラリティをロックした.
- 証拠は,単一のフォトスイッチの閉鎖は,キラルゲストをケージから追い出すのに十分であると示唆しています.
結論:
- この研究は,DTEのケージにおける光異性化の中間段階に関する前例のない洞察を提供します.
- ゲストは最初のフォトスイッチの閉鎖時に排出され,完全なケージの変換を必要としません.
- DTEリガンドの固有のキラリティは,光異性化とゲストダイナミクスのモニタリングのための効果的なレポーターとして機能する.
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