CAS-Climate: Supramolecular Control of Reactivity in the Solid State: From Metal-Free Photoswitches and Click Reactivity to Manufacturing Diverse Molecules

CAS-Climate：固态反应性的超分子控制：从无金属光电开关和点击反应性到制造多种分子

• 批准号: 2221086
• 负责人: Alexei Tivanski
• 金额: $ 50万
• 依托单位: University of Iowa
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-15 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2221086&HistoricalAwards=false
• 关键词: CAS; Climate; Supramolecular; Control; Reactivity

Nontechnical Abstract: This project, with support from the Solid State and Materials Chemistry program in NSF’s Division of Materials Research, aims to advance the understanding of, and enhance the value of, reactions performed in the organic solid state. These new insights benefits materials researchers and synthetic chemists alike. Reactions performed in organic solids are relevant to the field of green chemistry: they are highly selective, high-yielding, and solvent-free. Reactions performed in organic solids can also be used to store chemical energy, which makes the solids valuable to develop materials for applications in sustainability. The potential of the organic solid state to be used as a medium to perform synthetic chemistry and develop sustainable materials, however, has been severely hampered by a lack of a general method to orient reactive groups into the proper geometry to undergo a chemical reaction. Professor MacGillivray and his research group make use of noncovalent bonds (e.g. hydrogen bonds) in a general way to guide the assembly of molecules in crystals so that reactive groups are properly and reliably aligned to undergo reaction. Thereby they study the scope of starting materials that react in the solid state and how to eventually manufacture a wide variety of molecules and materials as products. The research has the potential to lay the foundation for a “greener” manufacturing approach for the chemical industry where reactions can be performed using purely organic solids without the use of metals or metal ions. As part of the project’s outreach activities, high-school students are introduced to noncovalent bonding and organic solid-state chemistry. The principal investigator also involves students from underrepresented groups in the research activities, maintains active collaborations with undergraduate colleges, and engages middle-school students to promote careers in chemical science (e.g. X-ray crystallography). Technical Abstract: The project, supported by the Solid State and Materials Chemistry program in NSF’s Division of Materials Research, makes reactions performed in the organic solid state more valuable to synthetic chemists and materials scientists by developing solids that form the basis of functional materials and expand the scope of reactions and products. Specifically, the researchers study (i) their potential as metal-free organic switches, (ii) uses of cocrystals to perform metal-free ‘click’ reactions, and (iii) an approach to generate broad ranges of molecules. Photochromic switches are designed using hydrogen-bond-directed self-assembly that direct intermolecular [2+2] photodimerizations. The click reactions are conducted with the assistance of perfluorophenyl-phenyl interactions to generate extended pi-conjugated molecules. Broad ranges of molecules are synthesized in crystals using post-synthetic modifications of cyclobutanes functionalized with aryl nitriles. The research is motivated by the fact that although the organic solid state is a highly attractive medium to perform chemical reactions to make (and break) covalent bonds, there remains a lack of general methodologies to perform reactions ‘at will’ akin to the liquid phase. Outcomes of this research are expected to enable a broader application of reactions in solids to problems and challenges of organic synthesis (e.g. complex molecules, additional chemical reactions), green chemistry (e.g. solvent-free preparation), and materials science (e.g. single-crystal switches).This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

摘要：本项目由美国国家科学基金会材料研究部固态与材料化学项目资助，旨在促进对有机固态反应的理解，并提高其研究价值。这些新发现对材料研究人员和合成化学家都有好处。在有机固体中进行的反应与绿色化学领域有关：它们具有高选择性、高收率和无溶剂性。在有机固体中进行的反应也可以用来储存化学能，这使得固体对开发可持续性应用的材料有价值。然而，由于缺乏一种将反应基团定向到适当的几何形状以进行化学反应的通用方法，有机固体作为进行合成化学和开发可持续材料的介质的潜力受到了严重的阻碍。MacGillivray教授和他的研究小组一般利用非共价键（例如氢键）来指导晶体中分子的组装，从而使反应基团正确可靠地排列以进行反应。因此，他们研究在固体状态下反应的起始材料的范围，以及如何最终制造各种各样的分子和材料作为产品。这项研究有可能为化学工业的“绿色”制造方法奠定基础，在化学工业中，反应可以使用纯有机固体而不使用金属或金属离子。作为项目推广活动的一部分，学生们将学习非共价键和有机固态化学。首席研究员还让来自代表性不足群体的学生参与研究活动，与本科院校保持积极合作，并吸引中学生参与化学科学（例如x射线晶体学）的职业发展。技术摘要：该项目由美国国家科学基金会材料研究部固态与材料化学项目支持，通过开发固体来形成功能材料的基础，扩大反应和产物的范围，使有机固态反应对合成化学家和材料科学家更有价值。具体来说，研究人员研究了(i)它们作为无金属有机开关的潜力，（ii）使用共晶进行无金属的“点击”反应，以及（iii）一种产生广泛分子的方法。光致变色开关采用氢键定向自组装设计，直接进行分子间[2+2]光二聚化。在全氟苯基-苯基相互作用的帮助下进行了键合反应，生成了扩展的π共轭分子。广泛的分子在晶体中合成使用环丁烷与芳基腈功能化后的合成修饰。这项研究的动机是，尽管有机固体是一种非常有吸引力的介质，可以进行化学反应来形成（和破坏）共价键，但仍然缺乏类似于液相的“随意”进行反应的通用方法。这项研究的结果有望使固体反应更广泛地应用于有机合成（如复杂分子，附加化学反应），绿色化学（如无溶剂制备）和材料科学（如单晶开关）的问题和挑战。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

The formation and stability of fluoxetine HCl cocrystals investigated by multicomponent milling

多组分研磨研究盐酸氟西汀共晶的形成和稳定性

• DOI: 10.1039/d2ce01341j
• 发表时间: 2023
• 期刊: CrystEngComm
• 影响因子: 3.1
• 作者: Peach, Austin A.;Holmes, Sean T.;MacGillivray, Leonard R.;Schurko, Robert W.
• 通讯作者: Schurko, Robert W.

Hydrogen and halogen bonds in drug-drug cocrystals of X-uracil (X = F, I) and lamivudine: extended quadruplex and layered assemblies

• DOI: 10.1080/10610278.2022.2163644
• 发表时间: 2021-12
• 期刊: Supramolecular Chemistry
• 影响因子: 3.3
• 作者: Chang-Zhi Li;E. Keene;Celymar Ortiz-de León;Leonard R. MacGillivray