Supramolecular Approaches to Control Reactivity in the Organic Solid State

摘要：本项目的总体目标是提高在有机固体状态下进行的化学反应的价值。合成化学是化学科学的基础，它使社会进步与开发新药（如活性药物）和技术重要材料（如强而轻）有关。这个项目将开发策略来合成分子，其中化学反应在固体状态下进行。合成化学通常在液相或溶液中进行，而固态的无溶剂和“冷冻”环境为合成具有独特结构和性质的分子提供了机会。因此，在有机固体中进行反应的策略可以加速合成化学如何定义并应用于社会和技术发展的进展。该项目将整合代表性不足的群体，发展本科实验室实验，并与本科学院保持积极合作。该项目还将向中学生介绍化学科学方面的职业（例如x射线晶体学）。技术摘要：该项目将通过开发固体反应，产生具有合成价值的有机官能团和/或基于降低对称性的产物，从而提高在固体中进行的反应的价值。该研究将应用多组分固体共晶和/或金属有机材料的形式来指导固态反应。具体来说，(i)金属有机固体将指导亚胺的光二聚化，形成仅与醛基排列的环丁烷，（ii）共晶体将指导光二聚化，产生不对称的ladderanes，以及（iii）共晶体将支持交叉光环加成。这项研究的动机是，尽管多组分固体正迅速成为可靠地控制固体相对于液相反应性的介质，但基于形成具有挑战性的有机官能团和降低对称性的产品的重要研究途径仍未得到解决。当拟议的研究完成后，将有可能更广泛地将固体中的反应应用于有机合成（如复杂分子）、绿色化学（如无溶剂制备）、无机化学（如金属-有机反应性）和材料科学（如单晶反应）等问题。

Nontechnical Abstract:The general goal of this project is to increase the value of chemical reactions conducted in the organic solid state. Synthetic chemistry is an underpinning in chemical science that enables advancements in society as related to developing new medicines (e.g. active pharmaceutics) and technologically-important materials (e.g. strong and lightweight). This project will develop strategies to synthesize molecules in which chemical reactions are conducted in the solid state. Whereas synthetic chemistry is typically performed in the liquid phase or solution, the solvent-free and "frozen" environment of the solid state provides opportunities to synthesize molecules with unique structures and properties. Strategies to conduct reactions in organic solids can, thereby, accelerate progress of how synthetic chemistry defines and is applied to developments in society and technology. The project will integrate underrepresented groups, develop undergraduate laboratory experiments, and maintain active collaborations with undergraduate colleges. The project will also introduce middle-school students to careers in chemical science (e.g. X-ray crystallography).Technical Abstract:This project will increase the value of reactions conducted in solids by developing solid-state reactions that generate products with synthetically-valuable organic functional groups and/or are based on reduced symmetries. The research will apply multi-component solids in the form of cocrystals and/or metal-organic materials to direct the solid-state reactions. Specifically, (i) metal-organic solids will direct photodimerizations of imines that form cyclobutanes lined exclusively with aldehyde groups, (ii) cocrystals will direct photodimerizations that generate unsymmetrical ladderanes, and (iii) cocrystals will support cross-photocycloadditions. The research is motivated by the fact that although multi-component solids are rapidly emerging as media to reliably control reactivity in solids relative to the liquid phase, important avenues of needed investigation based on forming products decorated with challenging organic functional groups and of reduced symmetry remain unaddressed. When the proposed research is completed, it will be possible to more broadly apply reactions in solids to problems of organic synthesis (e.g. complex molecules), green chemistry (e.g. solvent-free preparation), inorganic chemistry (e.g. metal-organic reactivity), and materials science (e.g. single-crystal reactions).