Interpenetrating coordination cages: Understanding of formation and guest binding, application as multitopic organizational units and aggregation into higher order structures

相互渗透的协调笼：理解形成和客体绑定、作为多主题组织单元的应用以及聚合成更高阶的结构

• 批准号: 231349046
• 负责人: Professor Dr. Guido Clever
• 金额: --
• 依托单位: Lehrstuhl für Bioanorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/231349046?language=en
• 关键词: Interpenetrating; coordination; cages; Understanding; formation

Metal-mediated self-assembly of supramolecular structures allows for step-wise approaching the structural and functional complexity of biological nano structures. Coordination cages with their inner cavity show potential to study basic features of host-guest phenomena, mechanical transformations and stimuli-responsive behaviour. Possible applications include selective recognition, catalysis, molecular electronics and smart materials. With a focus on palladium-based monomeric and dimeric cages, the first funding period has delivered a plethora of new data on cage formation, switchable guest uptake, and dynamic behaviour of the systems. Nevertheless, several questions remained open and new ideas and approaches have emerged. The elongation will divide the project into two sub areas: 1. Mechanistic studies of cage formation/dimerization and guest binding as well as synthetic modification of the donor functionalities. In addition, the synthesis of heterobimetallic cages shall be implemented, both via introduction of orthogonal donor sites as well as via application of kinetic effects. 2. The elaborated principles on cage formation, stability, guest binding, mechanical transformation and ligand-centred derivatisation will be applied in the form of functional systems. We have selected three major goals: a) Synthesis of amphiphilic cages, carrying long, if necessary branched, chains of different polarity in equatorial and/or terminal positions and examination of their aggregation behaviour and material properties in solution and bulk compounds. b) Extension of the (spectro-)electrochemical characterization of cages based on redox active ligands (e.g. oligothiophenes, methylene blue, fuchsone ...) aimed at finding further suitable redox pairs for the light-induced charge separation. c) Further studies on the assembly of chiral cages and their propensity for enantioselective guest binding and effect on chemical reactions.

金属介导的超分子结构的自组装允许逐步接近生物纳米结构的结构和功能的复杂性。配位笼及其内腔显示出研究主客体现象、机械转换和刺激响应行为的基本特征的潜力。可能的应用包括选择性识别、催化、分子电子学和智能材料。由于重点关注钯基单体和二聚体笼，第一个资助期提供了大量有关笼形成、可切换客体吸收和系统动态行为的新数据。尽管如此，仍有若干问题有待解决，并出现了新的想法和办法。延伸将项目分为两个子区域：1。笼形成/二聚化和客体结合以及供体官能团的合成修饰的机理研究。此外，杂环笼的合成应通过引入正交供体位点以及通过应用动力学效应来实现。2.笼的形成，稳定性，客体结合，机械转化和配体为中心的衍生化的详细原则将适用于功能系统的形式。我们已经选择了三个主要目标：a）两亲性笼的合成，携带长的，如果必要的分支，在赤道和/或终端位置的不同极性的链，并检查其聚集行为和材料性质的溶液和散装化合物。B）基于氧化还原活性配体（例如低聚噻吩、亚甲蓝、品红.）旨在发现用于光诱导电荷分离的进一步合适的氧化还原对。c）进一步研究手性笼的组装及其对映选择性客体结合的倾向和对化学反应的影响。