Pfrunder Michael C, Marshall David L, Poad Berwyck L J, Stovell Ethan G, Loomans Benjamin I, Blinco James P, Blanksby Stephen J, McMurtrie John C, Mullen Kathleen M
Centre for Materials Science (CFMS), Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland, 4000, Australia.
School of Chemistry and Physics, Queensland University of Technology, 2 George Street, Brisbane, Queensland, 4000, Australia.
Angew Chem Int Ed Engl. 2022 Nov 7;61(45):e202212710. doi: 10.1002/anie.202212710. Epub 2022 Oct 7.
Coordination cages with well-defined cavities show great promise in the field of catalysis on account of their unique combination of molecular confinement effects and transition-metal redox chemistry. Here, three coordination cages are reduced from their native 16 oxidation state to the 2 state in the gas phase without observable structural degradation. Using this method, the reaction rate constants for each reduction step were determined, with no noticeable differences arising following either the incorporation of a C -fullerene guest or alteration of the cage chemical structure. The reactivity of highly reduced cage species toward molecular oxygen is "switched-on" after a threshold number of reduction steps, which is influenced by guest molecules and the structure of cage components. These new experimental approaches provide a unique window to explore the chemistry of highly-reduced cage species that can be modulated by altering their structures and encapsulated guest species.
具有明确空腔的配位笼由于其分子限域效应和过渡金属氧化还原化学的独特结合，在催化领域显示出巨大的潜力。在此，三个配位笼在气相中从其天然的 +16 氧化态还原为 +2 态，且没有可观察到的结构降解。使用这种方法，确定了每个还原步骤的反应速率常数，在引入 C -富勒烯客体或改变笼的化学结构后均未出现明显差异。经过一定数量的还原步骤后，高度还原的笼状物种对分子氧的反应活性被“开启”，这受到客体分子和笼组分结构的影响。这些新的实验方法为探索高度还原的笼状物种的化学性质提供了一个独特的窗口，这种化学性质可以通过改变其结构和封装的客体物种来调节。
