INTRAMOLECULAR ELECTRON TRANSFER IN PORPHYRIN DIMERS, TIMERS AND PENTAMERS

本子项目是利用由NIH/NCRR资助的中心赠款提供的资源的众多研究子项目之一。子项目和研究者（PI）可能已经从另一个NIH来源获得了主要资金，因此可以在其他CRISP条目中表示。列出的机构是中心的，不一定是研究者的机构。电子转移过程中给体和受体之间电子耦合的性质是决定反应速率和产率的重要考虑因素。在这类系统中，给体和受体之间的物理耦合很可能在电子耦合中也起着相关的作用。为了研究物理耦合对电子耦合的影响，从而研究电子转移速率常数，我们研究了电子转移反应驱动力基本不变但电子转移伙伴之间的物理耦合不同的化合物。具体来说，我们已经合成了一系列金属卟啉系统，这些系统由一系列苯基环间隔剂连接的电子给体和受体对组成，这些间隔剂要么与卟啉环共价连接，要么与卟啉环中所含的金属轴向配位。

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. 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.