在使用交叉结合桥梁的捐赠-桥梁-接受分子中控制电子转移
Annie Butler Ricks1, Gemma C Solomon, Michael T Colvin
1Department of Chemistry and Argonne-Northwestern Solar Energy Research Center, Northwestern University, Evanston, Illinois 60208-3113, United States.
Journal of the American Chemical Society
|October 15, 2010
概括
相比于线性桥梁,光启动的电荷分离 (CS) 通过交叉结合的桥梁显著较慢,这表明向西格玛通路的转变. 这影响了捐赠-桥梁-受体分子中的电子转移动态.
科学领域:
- 摄影化学的使用.
- 分子电子学分子电子学
- 有机化学 有机化学
背景情况:
- 捐赠者-桥梁-接受者 (D-B-A) 分子对于理解电荷分离 (CS) 和重组 (CR) 是至关重要的.
- 桥梁的电子特性显著影响CS和CR过程的效率.
研究的目的:
- 为了比较和对比D-B-A分子中的光启动的CS和CR,具有不同的桥 (交叉合,线性合,和).
- 调查桥梁结构对电子传输速率和电子合的作用.
主要方法:
- 时间分辨率光谱被用来研究CS和CR动态.
- 进行了分子导电率计算,以分析通桥电子合.
主要成果:
- 通过交叉结合的1,1-二乙烯桥的CS速度比通过其线性跨stilbene对应物慢30倍,与和二甲桥相比.
- 通过交叉结合的桑桥的CS显示了与其线性跨-stilbene对应物相似的速率.
- 分子导电计算揭示了交叉合系统中的量子干扰效应,改变了电子合.
结论:
- 交叉结合显著降低了对捐赠器-接受器电子合的pi轨道贡献,有利于CS的西格玛通路.
- 交叉合桥的量子干扰效应调节电子合,与实验电子传输速率趋势保持一致.
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