塩素フィルの20位経由の分子内電子移転 分子内電子移転 分子内電子移転 分子内電子移転 分子内電子移転 分子内電子移転 分子内電子移転 分子内電子移転
Richard F Kelley1, Michael J Tauber, Michael R Wasielewski
1Department of Chemistry and International Institute of Nanotechnology, Northwestern University, Evanston, Illinois 60208-3113, USA.
Journal of the American Chemical Society
|April 6, 2006
まとめ
新しいクロロフィルa誘導体 (ZCPh) が合成され,ドナー-受容体ダイアードで研究されました. 構造的な違いにもかかわらず,ZCPhとポルフィリン二酸化物は,電荷の再分配により,同様の電子伝送率を示しています.
科学分野:
- フォトケミストリー フォトケミストリー
- オーガニック・シンセシス オーガニック・シンセシス
- スペクトル顕微鏡検査です.
背景:
- クロロフィルおよびその誘導体は,光採集および電子移転プロセスを理解する上で極めて重要です.
- ドナー-受容体ダイアードは,光誘導による電荷分離と再結合を研究するためのモデルシステムです.
- マクロサイクルドナーの電子的および構造的性質は,電荷移転のダイナミクスに影響を与えます.
研究 の 目的:
- スズキクロスカップリングによる新しい20-フェニル置換クロロフィルa誘導体 (ZCPh) の合成.
- ZCPhベースのドナー-受容体二酸化物における光誘導電子伝送ダイナミクスを調査する.
- 電子結合と電荷伝送速度を,類似のポルフィリン基ダイアッドと比較するために.
主な方法:
- ZCPh.を合成するためのスズキクロスカップリング反応.
- ナフタレンまたはペリレンビス ((ディカルボキシミド) 受容体を含むドナー受容体ダイアードの合成.
- 電子パラマグネティック共振 (EPR) と電子核二重共振 (ENDOR) のスペクトロスコーピー.
- 密度関数理論 (DFT) による計算.
主要な成果:
- ZCPh誘導体は,クロロフィールa.から良好な収穫量で合成されました.
- 放射光学および計算分析により,ZCPh根カチオンの最も高い占有分子軌道 (HOMO) は,C20位置で最小のスピン密度を持っていることが明らかになりました.
- DFTの計算では,受容体の負の電荷は,ZCPhとポルフィリン基のカチオンの両方の電荷密度をフェニル環に大幅にシフトすることを示しました.
- この電荷再配分は,ほぼ同一の電子結合マトリックス要素 (V) と類似の電子伝送率につながります.
結論:
- 合成されたZCPh誘導体は,ドナー-受容体システムの効果的な構成要素です.
- ラジカルカチオンにおけるスピン密度分布の違いにもかかわらず,ZCPhとポルフィリン二酸化物における電子結合と電子伝送率は比較可能です.
- 受容体の負の電荷の接近が電子結合を決定し,ドナーの固有の差異を最小限に抑えます.
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