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

用于光致变色和电致变色分子尺度器件的异双核杯芳烃基金属配合物

• 批准号: 34631931
• 负责人: Dr. Margit Gruner
• 金额: --
• 依托单位: Professur für Organische Chemie II
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2007
• 资助国家: 德国
• 起止时间: 2006-12-31 至 2009-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/34631931?language=en
• 关键词: Heterobinuclear; calixarene; based; metal; complexes

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.

该项目旨在设计、合成、结构和物理化学研究杯芳烃衍生物及其金属配合物用于新的分子器件。将开发光和电压驱动的分子器件，其中光和电活性物质通过杯芳烃平台分离。它计划合成杯芳烃衍生物的功能基团的上，下边缘的两个活性物种，能够执行电子（能量）转移过程的结合，并研究其配置和构象，以及他们的动态主客体行为，使用现代方法梯度一维和二维核磁共振（NMR）。过渡金属离子被设想为光活性和电活性物质。该项目是基于开发杯芳烃基质的两个边缘，用于c/（/）-金属离子及其络合物的内球和外球配位。金属配合物的外层配位是通过配合物与杯芳烃的正（负）电荷边缘之间的协同静电作用和货车范德华相互作用实现的。杯芳烃的内球配位主要是通过CN、OH、NH_2、COOH对杯芳烃下缘的修饰来实现的。在该项目的过程中，它的目的是合成metat-杯芳烃-金属分子系统与各种长度的杯芳烃桥，并研究金属到金属的距离对金属离子中心之间的电子（能量）转移的影响。这两个动力学测量和结构和动态NMR调查将适用于这些目的。杯芳烃基质的伸长将通过改变下缘取代基来实现。