Kinetically Viable Pathways for Multitopic DCC

多主题 DCC 的动力学可行途径

• 批准号: 1610328
• 负责人: Jeffrey Moore
• 金额: $ 50.05万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-15 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1610328&HistoricalAwards=false
• 关键词: Kinetically; Viable; Pathways; Multitopic; DCC

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).

在这个由化学系大分子、超分子和纳米化学项目资助的项目中，Jeffrey S。伊利诺伊大学香槟分校化学系的摩尔正在开发化学合成新的，形状持久的，碳基笼状分子。 他正在研究将小的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，三维结构包含长度为几纳米量级的空隙，并且具有持久的形状，因此这些结构可以隔离其他小分子。 教授摩尔和他的研究小组继续参加几个辅导和推广活动，沟通科学进步的重要性，以K-12观众和公众。 他们参与了具体的方案，如鼓励明天的化学家（ETC）和伊利诺伊州女工程师在学术界的培训（iFEAT）。摩尔教授正在探索合成方法，以构建具有明确空腔的笼状分子，用于主客体相互作用，吸附，分离和稳定反应中间体。 该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所需的结果，或者不能产生可辨别的产品。 在这个项目中，摩尔教授正在开发实验方法，以探测动态共价化学（DCC）的能源景观，并利用这些信息制定战略，直接DCC前体沿着动力学可行的途径，同时避免不必要的动力学陷阱。 正在使用的特定DCC方法是炔复分解，并且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，什么设计策略将引导DCC沿着动力学上可行的途径，以及用于构建2维结构的策略如何适应于3维笼的合成。 从这个项目中获得的知识预计将直接涉及到其他重要类别的材料，如共价有机框架（COFs）的建设。

项目成果

Quantifying Error Correction through a Rule-Based Model of Strand Escape from an [ n ]-Rung Ladder

通过基于规则的 [ n ] 梯级链逃逸模型量化纠错

• DOI: 10.1021/jacs.9b08958
• 发表时间: 2019
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Cencer, Morgan M.;Greenlee, Andrew J.;Moore, Jeffrey S.
• 通讯作者: Moore, Jeffrey S.