Functional metallo-supramolecular polyelectrolyte systems: Synthesis, structure and properties in solution

在高分子化学（Schubert）和高分子物理（Tsvetkov）两个小组拟议的联合项目中，目标是制备带电侧链金属聚合物及其在溶液中的分子和构象分析。申请人的目标是基本了解金属聚合物的各种结构参数（金属中心的性质，电荷，反离子等的存在）如何影响其溶液性质。为此，三种不同类型的金属聚合物将成为关注的焦点：具有三元吡啶配合物的金属聚合物，茂金属/茂金属位点和金属-羰基配合物。这些聚合物对于（光）催化、光电、纳米技术或生物医学应用具有重要意义。然而，对其性能与分子结构和构象结构之间的关系还没有深入的研究。合成的模块化，结合了可控自由基聚合技术和金属-配位化学，将允许精确制备一套系统的金属聚合物文库（舒伯特基团），这些文库需要通过Tsvetkov基团中可用的各种流体动力学和光学方法进行分析。申请人已同意与两个外部合作伙伴合作，进一步利用合成的金属聚合物制造用于数据存储应用的双金属纳米颗粒（Wong group, Hong Kong， P.R. China）和光活性抗菌金属药物（Schatzschneider group, w<s:1> rzburg, Germany）。最后，聚电解质间配合物，即制备的聚阳离子金属聚合物和天然或合成的聚阴离子的超分子缔合物，将被组装并相应地表征。

In the proposed joint project between the two groups from polymer chemistry (Schubert) and polymer physics (Tsvetkov) the preparation of charged side-chain metallopolymers and their molecular and conformational analysis in solution is targeted. The applicants aim for a fundamental understanding of how the various structural parameters of the metallopolymers (nature of the metal center, presence of charges, counterions, etc.) contribute to their solution properties. For this purpose, three different types of metallopolymers will be in focus of interest: Metallopolymers with pending terpyridine complexes, metallocene/metallocenium sites and metal-carbonyl complexes. Such polymers are of significant importance regarding, for instance, (photo)catalytic, optoelectronic, nanotechnological or biomedical applications. However, in-depth investigations correlating their performance to their molecular and conformational structure have not yet been made. The modularity of synthesis, combining controlled radical polymerization techniques and metal-to-ligand coordination chemistry, will allow an accurate preparation of a systematic set of metallopolymer libraries (Schubert group) required for the analysis by the various hydrodynamic and optical methods available in the Tsvetkov group. The applicants have agreed cooperation with two external partners to further utilize the synthesized metallopolymers to fabricate bimetallic nanoparticles for data-storage applications (Wong group, Hong Kong, P.R. China) and as photoactive antimicrobial metallodrugs (Schatzschneider group, Würzburg, Germany).Finally, interpolyelectrolyte complexes, the supramolecular associates of the prepared polycationic metallopolymers and natural or synthetic polyanions, will be assembled and characterized accordingly.