ENERGY & CHARGE MIGRATION & ANNIHILATION IN MULTICHROMOPHORIC NANOSTRUCTURES

观察到的复杂分子光过程 光合作用/光伏设备，如能量迁移和 湮灭、功能光开关和空间扩展 电子转移，不发生在孤立的分子中，但需要 通信亚单位的化学整合。该计划的目的是 拟议的项目是建造新颖、多功能、 溶液中四聚吡咯化合物的超分子阵列，以及 表征其静态和动态的物理化学性质 关于能量迁移和电子转移机制，AS 以及它们与分子氧的失活相互作用和 激发态的有机猝灭剂。通过静态和静态的方法 动态荧光和磷光光谱，瞬变 吸收光谱(毫秒-飞秒时间分辨率)和计算 原子核和电子结构的分子模拟 电子能激发失活的机理，以及电子能激发失活 启用色间通信的进程将是 在扩展的卟啉组件中进行了研究。我们将特别注意 被提供给组件之间的分子间相互作用， 分子氧和其他激发态猝灭剂。这些结构 要合成和研究的包括一系列共价化合物 连接的化学二聚体和三聚体以及自组装 具有额外活性生色团的非共价结合阵列。 项目成果可能的市场应用包括： (1)单线态分子光化学传感器的辅助设计 氧气，以及(2)光动力癌症治疗的进展。

The complex molecular photoprocesses observed in photosynthetic/photovoltaic devices, such as energy migration and annihilation, functional photoswitching, and spatially extended electron transfer, occur not in isolated molecules, but require chemical integration of communicating subunits. The aim of the proposed project is to construct novel, multifunctional, supramolecular arrays of tetrapyrrolic compounds in solution, and characterize their stationary and dynamic physio-chemical properties with respect to energy migration and electron transfer mechanisms, as well as their deactivating interactions with molecular oxygen and organic quenchers of excited states. By the methods of stationary and kinetic fluorescent and phosphorescent spectroscopy, transient absorption spectroscopy (ms-fs time resolution), and computational molecular modeling of nuclear and electronic structure, the principal mechanisms of electronic energy excitation deactivation, and the processes which enable interchromophoric communication, will be studied in extended porphyrin assemblies. Particular attention will be afforded to the intermolecular interactions between the assemblies, molecular oxygen, and other excited state quenchers. The structures to be synthesized and investigated include a range of covalently linked chemical dimers and trimers, as well as self-assembling non-covalently bound arrays with additional active chromophores. Possible market applications of the project results would include: (1) aid in the design of molecular photochemical sensors of singlet oxygen, and (2) development in photodynamic cancer therapy.