INTERMOLECULAR ELECTRON TRANSFER IN PORPHYRIN DIMERS

供体和受体之间电子耦合的本质 在电子转移过程中是一个重要的考虑因素 确定这种反应的速率，从而确定其产率。它 很可能捐赠者和接受者之间的物理耦合也 在这类系统的电子耦合中起着重要的作用。在……里面 为了研究物理耦合对电磁场的影响。 电子耦合，因此电子转移速率常数，我们 正在研究的化合物中，电子的驱动力 转移反应基本上保持不变，但物理反应 电子转移伙伴之间的耦合是不同的。具体来说，我们 合成了一系列金属卟啉体系，它们包括 电子给体和受体对由一系列的 苯环间隔物或者共价连接到 卟啉环或轴向配位到金属中所含 卟啉环。正向和反向电子转移的速率 用飞秒泵浦探测光谱和TCSPC进行了测量 (时间相关单光子计数)。我们得出的结论是 电子转移速率常数确实存在差异 这反映了供体和受体的物理耦合 半个。

The nature of the electronic coupling between donors and acceptors in electron transfer processes is an important consideration in determining the rates and therefore the yields of such reactions. It is likely that the physical coupling between donors and acceptors also plays a pertinent role in the electronic coupling in such systems. In order to investigate the effect of the physical coupling on the electronic coupling, hence the electron transfer rate constants, we are studying compounds in which the driving force for electron transfer reaction remains essentially constant but the physical coupling between electron transfer partners differs. Specifically, we have synthesized a series of metallo-porphyrin systems which consist of an electron donor and acceptor pair linked by a series of phenyl-ring spacers which are either covalently linked to the porphyrin ring or coordinated axially to the metal contained in the porphyrin ring. The rates for forward and reverse electron transfer have been measured by femtosecond pump-probe spectroscopy and TCSPC (time correlated single photon counting). We have concluded that there is, indeed a difference in the electron transfer rate constants which reflects the physical coupling of the donor and acceptor moieties.