Phosphorus and molecular materials

有机齐聚物和有机聚合物已成功地应用于电光器件(场效应晶体管、有机发光二极管)中的有源元件。这些器件的性能与分子有机材料的电子性质以及它们在固态中的有序性有关。因此，在分子水平上调节共轭体系的电子结构并控制其结构顺序，对于开发改进的新材料至关重要。该项目建议开发一种新型的包含磷环的共轭体系。P-杂环的存在潜在地提供了几种控制这些体系的组织和电子性质的方法。我们首次提出通过剪裁垂直于共轭主链的P-取代基来控制分子的排列。通过引入有序元素(长烷基链和烷氧基链，极性基团)，分子有望在液/固或水/气界面上自组装。反应性P原子的存在提供了另一种可能性，即通过过渡金属中心上的立体选择性配位使含磷低聚物有序。金属配位球的几何形状(正方形、平面体、八面体)可以得到不同的形状。具有不同电子性质(氧化态、轨道能级)的金属中心的引入将允许对共轭体系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、差示脉冲伏安法、光谱电化学)研究来阐明有价值的结构-性质关系。将进行荧光猝灭实验，以阐明含低聚物的金属络合物中的能量或电子转移过程。最后，对电聚合法制备电活性材料进行了探讨。具有传感器性能的含过渡金属的聚合物有望问世。

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.