新型配位驱动自组装磷光染料的构建及其在三重态湮灭上转换中的应用

项目名称： 新型配位驱动自组装磷光染料的构建及其在三重态湮灭上转换中的应用

项目编号： No.21302224

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 吴文婷

作者单位： 中国石油大学（华东）

项目金额： 25万元

中文摘要： 具有空穴结构的配位驱动自组装磷光染料，作为分子反应器在三重态湮灭上转换等领域具有广阔应用前景。传统分子反应器存在反应器的构型和尺度与反应物不匹配、可见光吸收弱和三重态寿命短（通常小于20 μs）等缺陷，限制了该类磷光染料的应用。鉴于磷光染料的光物理\光化学性质与其配体的激发态电子结构密切相关，本课题选择合适的荧光团（具有强可见光吸收的BODIPY）作为配体，以配位驱动自组装方法构建磷光染料，可同时调控磷光染料的构型和尺度，延长激发态寿命，增强可见光吸收能力，上述改进有利于提高上转换中磷光染料与能量受体之间三重态能量传递的效率以及处于三重态能量受体之间三重态湮灭的有效碰撞几率。借助量子化学计算辅助分子设计并对其光物理性质进行预测。通过研究紫外-可见吸收、磷光发射和瞬态吸收等光物理性质，建立有关强可见光吸收和长三重激发态寿命的配位驱动自组装磷光染料的知识体系。

中文关键词： 金属配合物；电子转移；能量传递；上转换；光氧化

英文摘要： Phosphorescent coordination-driven self assembly with cavity could be used as molecular reactors, which provide potential applications in triplet annihilation upconversion (TTA upconversion), etc. However, conventional molecular reactors have many drawbacks, such as unsuitable shape and size between the reactors and the reactants, weak visible light absorption, short lifetime of triplet excited state (usually shorter than 20 μs), which limit the applications of the phosphorescent complexes. The photophysical/photochemical properties of the phosphorescent complexes are closely related to the electronic structures of their ligands' excited states. In this project, the phosphorescent complexes are fabricated with appropriate fluorophores (e.g. BODIPY with intense absorption) as the bridge ligand and the coordination-driven self assembly as the corner connection. This design rationale is facile to tune the shape and size of the phosphorescent complexes, to prolong the triplet excited state lifetime, and to enhance the visible light absorption at the same time. These improvements will promote the efficiency of the energy transfer process of the triplet excited state, and the collision probability of the energy acceptors in triplet excited state. Herein, the DFT/TDDFT calculations help us design the molecular and pred

英文关键词： metal coordination complex；electron transfer；energy transfer；upconversion；photooxidation