Supramolecular Approaches to Control Reactivity in the Organic Solid State

非技术摘要：该项目的总体目标是增加在有机固体中进行的化学反应的价值。合成化学是化学科学的基础，它使社会在开发新药(例如活性药物)和技术上重要的材料(例如坚固和轻质)方面取得进步。该项目将开发合成在固态中进行化学反应的分子的策略。虽然合成化学通常在液体或溶液中进行，但固态的无溶剂和冻结环境提供了合成具有独特结构和性质的分子的机会。因此，在有机固体中进行反应的策略可以加快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，开发本科实验室实验，并保持与本科学院的积极合作。该项目还将向中学生介绍化学科学方面的职业(例如X射线结晶学)。技术摘要：该项目将通过开发产生具有合成价值的有机官能团和/或基于还原对称性的产品的固态反应来增加在固体中进行的反应的价值。这项研究将应用以共晶体和/或金属-有机材料形式的多组分固体来指导固态反应。具体地说，(I)金属-有机固体将指导亚胺的光二聚反应，形成专门以醛为基团的环丁烷；(Ii)共晶体将指导产生不对称梯烷的光二聚反应；(Iii)共晶体将支持交叉光环加成反应。这项研究的动机是这样一个事实，即尽管多组分固体正在迅速崛起，作为可靠地控制固体相对于液体的反应性的介质，但基于形成具有挑战性的有机官能团和对称性降低的产品所需研究的重要途径仍然没有得到解决。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(例如复杂分子)、绿色化学(例如无溶剂制备)、无机化学(例如金属-有机反应)和材料科学(例如单晶反应)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).