Heterobinuclear calixarene-based metal complexes for photo- and electrochromic molecular scale devices

本项目主要从事杯芳烃衍生物及其金属配合物的设计、合成、结构和物理化学研究。光和电压驱动的分子器件将被开发，其中光和电活性物质被杯芳烃平台分离。计划合成具有上下环官能团的杯芳烃衍生物，以结合两种能够进行电子（能量）转移过程的活性物质，并使用梯度1D和2D核磁共振（NMR）的现代方法研究它们的构型和构象以及它们的动态主客行为。过渡金属离子被设想为光活性和电活性物质。该项目的基础是利用杯芳烃基质的两个边缘来进行c/(/)-金属离子及其配合物的内球配位和外球配位。金属配合物的外球配位将通过金属配合物与杯芳烃带正电（负电）的环之间的静电和范德华相互作用来实现。杯芳烃下缘的CN、OH、NH2、COOH基团的修饰将控制杯芳烃的内球配位。在项目过程中，拟合成具有不同长度杯芳烃桥的元杯芳烃-金属分子体系，并研究金属间距离对金属离子中心之间电子（能量）转移的影响。动力学测量和结构和动态核磁共振研究将应用于这些目的。杯芳烃基体的伸长是通过改变下环取代基来实现的。

The project is directed to the design, synthesis, structural and physico-chemical investigation of calixarene derivatives and their metal complexes for new molecular devices. Photo- and voltage-driven molecular devices will be developed, wherein the photo- and electro active species are separated by a calixarene platform. It is planned to synthesize calixarene derivatives with functional groups both on the upper and lower rims for the binding of two active species which are able to perform electron (energy) transfer processes and to investigate their configuration and conformation as well as their dynamic host-guest behaviour using modern methods of gradient 1D and 2D nuclear magnetic resonance (NMR). Transition metal ions are envisaged as photo- and electro-active species. The project is based on an exploitation of both rims of the calixarene matrix for inner- and an outer-sphere coordination of c/(/)-metal ions and their complexes. The outersphere coordination of metal complexes will be achieved by cooperative electrostatic and Van der Waals interactions between metal complexes and positively (negatively) charged rims of the calixarenes. The inner-sphere coordination will be governed by the modification of the lower rim of calixarenes with CN, OH, NH2, COOH moieties. In the course of the project it is intended to synthesize metat-calixarene-metal molecular systems with various lengths of the calixarene bridge and to investigate the influence of the metal to metal distance on the electron (energy) transfer between the metal ion centres. Both kinetic measurements and structural and dynamic NMR investigations will be applied for these purposes. The elongation of the calixarene matrix will be realized by variation of the lower rim substituents.