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

该项目致力于用于新型分子器件的杯芳烃衍生物及其金属络合物的设计、合成、结构和物理化学研究。将开发光驱动和电压驱动的分子器件，其中光活性和电活性物种通过杯芳烃平台分离。本论文拟合成上、下环都带有官能团的杯芳烃衍生物，用于结合两个能够进行电子(能量)转移过程的活性物种，并用现代的梯度一维和二维核磁共振方法研究它们的构型和构象以及它们的动态主客体行为。过渡金属离子被认为是光活性和电活性物种。该项目的基础是开发杯芳烃基质的两个轮缘，用于c/(/)-金属离子及其络合物的内球配位和外球配位。金属络合物的外球配位是通过金属络合物与杯芳烃的正(负)电荷环之间的静电和范德华相互作用来实现的。杯芳烃的下缘用CN、OH、NH2、COOH基团修饰，将控制其内球配位。在这个项目的过程中，它旨在合成不同长度的杯芳烃桥的偏杯芳烃-金属分子体系，并研究金属到金属的距离对金属离子中心之间电子(能量)传递的影响。动力学测量以及结构和动态核磁共振研究都将用于这些目的。杯芳烃基质的伸长将通过改变下环取代基来实现。

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.