Functional Networks of Molecular Capsules

借鉴Nitschke小组在自组装金属有机笼材料，超分子组装的光诱导转化和系统化学领域的经验，拟议的研究将调查金属有机笼催化的潜在应用。金属-有机笼的组合能力，以创造预先组织的环境，空间限制活性物种，并可逆地组装/拆卸后，在条件的变化类似于那些利用酶来操纵反应动力学和提供新的模式的catalyst.The拟议的研究目前分为两个子项目：1。“光控可逆相转移的金属有机胶囊”，和2。“自组装M4 L 6笼内的光催化水活化”。在第一个子项目中，极性和非极性笼，在单独的相中并且相差一个配体子组分，在没有光的情况下会聚到极性笼，而光的存在驱动两者之间的平衡路径，其平衡分布有利于非极性笼。提出了水溶性四面体笼，其面向内的吡啶酮O-供体原子可以容纳彼此接近的4个Mn（III）离子。笼的顶点作为光氧化还原催化剂，相继氧化的Mn簇在光和终端氧化剂的存在下。能够穿过笼和/或结合到游离Mn配位位点的水然后可以被氧化成分子氧和质子，同时使Mn簇返回到其初始状态。

Drawing on experience in the Nitschke group in the areas of self-assembled metal-organic cage materials, light-induced transformations of supramolecular assemblies, and systems chemistry, the proposed research will investigate potential applications of metal-organic cages for catalysis. The combined abilities of metal-organic cages to create pre-organised environments, spatially confine reactive species, and to reversibly assemble/disassemble upon a change in conditions resemble those exploited by enzymes to manipulate reaction kinetics and provide opportunities for new modes of catalysis.The proposed research is currently divided into two sub-projects: 1. 'Light-controlled reversible phase transfer of metal-organic capsules', and 2. 'Photocatalytic water activation within a self-assembled M4L6 cage'.In the first, a polar and a non-polar cage, within separate phases and differing by one ligand subcomponent, converge to the polar cage in the absence of light, while the presence of light drives a pathway of equilibration between the two, whose equilibrium distribution favours the non-polar cage.In the second sub-project, an open, water-soluble tetrahedral cage is proposed whose inward-facing pyridone O-donor atoms may accommodate 4 Mn(III) ions in proximity to one another. The vertices of the cage serve as photoredox catalysts, successively oxidising the Mn cluster in the presence of light and a terminal oxidant. Water, capable of passing through the cage and/or binding to free Mn coordination sites may then be oxidised to dioxygen and protons, while returning the Mn cluster to its initial state.