Kinetically Viable Pathways for Multitopic DCC

在这个由化学系大分子、超分子和纳米化学计划资助的项目中，伊利诺伊大学厄巴纳-香槟分校化学系的Jeffrey S.Moore教授正在开发化学，以合成新的、形状持久的碳基笼形分子。他正在研究将小前体分子连接成更大的中空笼状结构的方法。从该项目中获得的知识将直接影响重要碳基材料的设计和合成。此外，这些三维结构含有几个纳米长的空洞，形状持久，因此这些结构可能会隔离其他小分子。摩尔教授和他的研究小组继续参加几项指导和外联活动，向K-12受众和普通公众宣传科学进步的重要性。她们参与了具体的计划，如鼓励明天的化学家(ETC)和伊利诺伊州女工程师在学术培训(IFEAT)。摩尔教授正在探索合成方法，以构建具有特定空穴的笼形分子，用于主客体相互作用、吸附、分离和稳定活性中间体。这一领域的典型方法是使用启发式的、以结构为中心的策略，并设计具有目标结构所需的适当几何形状的前体。然而，这种方法经常不能产生预期的结果，或者没有产生可识别的产品。在这个项目中，摩尔教授正在开发实验方法来探索动态共价化学(DCC)的能量景观，并利用这些信息来制定策略，以引导DCC前体沿着运动学上可行的途径，同时避免不受欢迎的动力学陷阱。目前正在使用的DCC方法是炔烃歧化反应，正在解决的具体问题包括动力学陷阱如何影响多主题DCC的结果，什么设计策略将指导DCC沿着运动学可行的途径进行，以及用于构建二维结构的策略如何适应三维笼子的合成。从该项目获得的知识预计将直接用于建造其他重要类别的材料，如共价有机骨架(COF)。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Professor Jeffrey S. Moore of the Department of Chemistry at the University of Illinois, Urbana-Champaign is developing chemistry to synthesize new, shape-persistent, carbon-based cage molecules. He is investigating methods to link small precursor molecules into larger, hollow cage-like structures. Knowledge obtained from this project will directly impact the design and synthesis of important carbon-based materials. In addition, the three-dimensional structures contain voids on the order of a few nanometers in length and with persistent shapes, so these structures may sequester other small molecules. Professor Moore and his research group continue to participate in several mentoring and outreach activities to communicate the importance of scientific advances to K-12 audiences and the general public. They are involved in specific programs such as Encouraging Tomorrow's Chemists (ETC) and the Illinois Female Engineers in Academia Training (iFEAT). Professor Moore is exploring synthetic methods to construct cage molecules with defined cavities for host-guest interactions, adsorption, separation, and stabilization of reactive intermediates. The typical approach in this field is to use a heuristic, structure-focused strategy and design precursors with the appropriate geometry required for a targeted structure. However, this method frequently fails to produce the desired outcome, or yields no discernable products. In this project, Professor Moore is developing experimental methods to probe dynamic covalent chemistry (DCC) energy landscapes and to use that information in formulating strategies to direct DCC precursors along kinetically viable pathways while avoiding undesirable kinetic traps. The particular DCC method being used is alkyne metathesis, and the specific issues being addressed include how kinetic traps affect the outcome of multitopic DCC, what design strategies will direct DCC along kinetically viable pathways, and how strategies used to construct 2-dimensional structures can be adapted to the synthesis of 3-dimensional cages. Knowledge gained from this project is expected to relate directly towards the construction of other important classes of materials such as covalent organic frameworks (COFs).