Molecular Design of Polymer Bilayer Films that Generate Rectifying Photocurrent

1.光诱导电子转移反应中电子流动的定向控制发生在无机半导体的整流结上。我们成功地观察到了两种聚乙烯亚胺薄膜的结点上的整流光氧化还原电流，其中一种薄膜由花菁染料组成，另一种由蒽醌组成。通过旋涂技术可以很容易地制备出聚合物双层膜。通过对含有一系列氧化还原电位不同的苯二酚的聚合物-花菁薄膜上观察到的光电流的详细比较，认为该聚合物薄膜体系中的光致电子转移速率可以用电子转移理论的“反转区”来解释。以N-甲基吩噻嗪为氧化还原物种，用电势阶跃方法研究了电子的自交换速率。结果表明，聚合物基质的性质对电子转移过程有很大的影响。

1. The directional control of electron flows in photo-induced electron transfer reactions is known to occur across a rectifying junction of inorganic semiconductors. We have succeeded in the observation of rectifying photoredox current on a junction of two polyethylenimine films, one consisting of merocyanine dyes and the other anthraquinone. The polymer bilayer film could easily be prepared by a spin-coating technique.2. From detailed comparison of the photocurrent observed on the polymer-merocyanine film containing a series of quinones with varying redox potentials, it was suggested that the photoinduced electron transfer rate in this polymer film system could be explicable by the "inverted region" of electron transfer theory.3. The self-exchange rate of electrons was investigated by a potential step method using a polymer film consisting of N-methylphenothiazine as a redox species. The result suggested that the nature of polymer matrices has a large effect on the electron transfer process.