Phosphorus and molecular materials

有机低聚物和聚合物已成功地作为有源元件应用于电光器件（场效应晶体管、有机发光二极管）。这些器件的性能与分子有机材料的电子特性及其在固体状态下的有序性有关。因此，调整共轭体系的电子结构并在分子水平上控制其结构顺序对于改进新材料的开发至关重要。该项目提出了一个新的家族的共轭系统纳入磷孔环的发展。p -杂环的存在可能提供几种方法来控制这些系统的组织和电子特性。我们首先提出通过剪裁垂直于共轭主链的磷取代基来控制分子排列。通过引入有序元素（长烷基链和烷氧基链、极性基团），期望分子在液/固或水/空气界面自组装。反应性p原子的存在提供的另一种可能性是通过过渡金属中心的立体选择配位对含磷寡聚物进行排序。不同的形状施加的几何金属配合球（方形平面，八面体等），可以得到。引入具有不同电子性质（氧化态，轨道能级）的金属中心将允许对共轭系统的光电性质进行微调。该项目的一个关键部分是通过UV/vis/nir，荧光和电化学（循环伏安法，差分脉冲伏安法，光谱电化学）研究阐明有价值的结构-性质关系。荧光猝灭实验将用于阐明含有低聚物的金属配合物中的能量或电子转移过程。最后，探讨电聚合法制备电活性材料。具有传感器特性的过渡金属聚合物是有希望的。

Organic oligomers and polymers have been applied successfully as active components in electro-optical devices (field effect transistors, organic light emitting diodes). The performance of these devices is related to electronic properties of the molecular organic material and their ordering in the solid state. Therefore, tuning the electronic structure of conjugated systems and controlling their structural order on the molecular level is crucial for the development of improved new materials. The project proposes the development of a novel family of conjugated systems incorporating phosphole rings. The presence of the P-heterocycles potentially offers several ways to control the organisation and the electronic properties of these systems. We first propose to control the molecular arrangement by tailoring the P-substituent of phospholes which is perpendicular to the conjugated backbone. Self-assembling of the molecules at the liquid/solid or water/air interface are expected by introduction of ordering elements (long alkyl and alkoxy chains, polar groups). Another possibility offered by the presence of the reactive P-atom is the ordering of phosphole-containing oligomers through stereoselective coordination on transition metal centers. Different shapes imposed by the geometry of the metal coordination sphere (square-planar, octahedral..), can be attained. The introduction of metal centers with different electronic properties (oxidation states, orbital levels) will allow a fine tuning of the opto-electronic properties of the conjugated systems. A crucial part of this project is the elucidation of valuable structure-properties relationships through UV/vis/nir, fluorescence and electrochemical (cyclic voltammetry, differential pulse voltammetry, spectroelectrochemistry) studies. Fluorescence quenching experiments will be conducted to elucidate energy or electron transfer processes in the metal complex containing oligomers. Finally, the preparation of electro-active materials by electropolymerisation will be explored. Transition metal-containing polymers with sensor properties are expected.