Collaborative Research: Porous Molecules as a Platform for Solid-State Organometallic Chemistry

合作研究：多孔分子作为固态有机金属化学的平台

基本信息

批准号：
2310682
负责人：
Eric Bloch
金额：
$ 9万
依托单位：
Indiana University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2023
资助国家：
美国
起止时间：
2023-01-15 至 2023-12-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2310682&HistoricalAwards=false
关键词：
Collaborative Research Porous Molecules Platform

项目摘要

With the support of the Chemical Synthesis program in the Division of Chemistry, Eric Bloch of the University of Delaware and David Powers of Texas A&M University will study new methods for the preparation of porous catalysts. Porous materials are widely used around the world for a wide variety of applications, including water filtration and/or softening, as desiccants, and in medicine. A subset of porous materials is used on a large scale in catalytic applications, including in the cracking of hydrocarbons. A key challenge in using porous materials as catalysts, however, is controlling and optimizing their reactivity where total surface area, structure type, and stability can play a role in determining their activity. The Bloch/Powers team is building on promising preliminary results to develop a new method for the synthesis of active porous catalysts by creating reactive salts. In this method, a charged nonporous reactive organometallic species will be combined with an oppositely-charged porous non-reactive ion to afford a new class of porous solids. It is envisioned that for porous materials so constructed catalytic activity will be finely tunable across a range of useful transformations including carbon-hydrogen bond functionalization and cross-coupling reactions. In addition to this, these studies will aid in the characterization of reactive species during catalytic transformations using the tools of in situ crystallography and spectroscopy. Drs. Bloch and Powers will continue to work to increase diversity in science by bringing excitement of synthetic chemistry research to a broad audience through local and regional educational experiences, including the development of an annual online school on X-ray powder diffraction for undergraduate and graduate students.This collaborative project is targeting the development of new porous materials for site-isolated and solid-state organometallic chemistry. While designer porous solids such as zeolites and metal-organic frameworks have shown incredible promise as heterogeneous catalysts, general platforms for the development of solid-state organometallic chemistry within confined spaces remain elusive. This work seeks to combine charged, permanently porous coordination cages with complementary-charged reactive organometallic fragments for the preparation of a new class of reactive catalysts, porous salts. During this funding period, Bloch and Powers will elucidate the general structure-function properties of porous salts where cage charge, geometry, and functional group presentation will be leveraged to tune salt structure and porosity. Subsequently, Bloch and Powers will use these salts as platforms to incorporate designer reactive ions into porous solids where small molecule binding and activation will be studied to assess salt activity. Reactions to be studied will include C-H bond functionalization and cross-coupling catalysis. Finally, the Bloch/Powers team will utilize straightforward layer-by-layer growth to prepare optically transparent, chemically addressable films which will be used for solid-state photochemical transformations.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.

在化学合成计划的支持下，特拉华大学的埃里克·布洛赫（Eric Bloch）和德克萨斯州A＆M大学的戴维·鲍尔斯（David Powers）将研究用于制备多孔催化剂的新方法。多孔材料在世界范围内广泛用于多种应用，包括水过滤和/或软化，作为干燥剂和药物。在催化应用中，包括在包括碳氢化合物的破裂中，大规模使用了多孔材料的子集。但是，在总表面积，结构类型和稳定性可以在确定其活性中发挥作用，使用多孔材料作为催化剂的关键挑战是控制和优化其反应性。 Bloch/Powers团队正在建立有希望的初步结果，以开发一种通过创建反应性盐来合成活性多孔催化剂的新方法。在这种方法中，带电的非孔反应性有机金属物种将与反对的多孔非反应性离子相结合，以提供新的多孔固体。可以预见的是，对于多孔材料，构建的催化活性将在一系列有用的转换中可调，包括碳氢键功能化和交叉偶联反应。除此之外，这些研究还将有助于使用原位晶体学和光谱学工具在催化转化过程中表征反应性物种。博士。 Bloch和Powers将通过本地和区域教育经验将合成化学研究的兴奋带给广泛受众，包括开发一年度在本科和研究生X射线粉末衍射的年度在线学校，以针对本科和研究生的X射线粉末衍射开发。尽管设计师多孔固体（例如沸石和金属有机框架）表现出令人难以置信的前景，但作为异质催化剂，但在狭窄空间内开发固态有机金属化学的一般平台仍然难以捉摸。这项工作旨在将带电的，永久性的多孔配位笼与互补的反应性有机金属碎片相结合，以制备新的反应性催化剂，多孔盐。在此资助期间，Bloch和Powers将阐明多孔盐的一般结构功能，其中笼子电荷，几何形状和功能组表现将被利用以调整盐结构和孔隙率。随后，Bloch和Powers将使用这些盐作为平台，将设计器的反应性离子掺入多孔固体中，其中将研究小分子结合和激活以评估盐活性。要研究的反应将包括C-H键功能化和交叉偶联催化。最后，Bloch/Powers团队将利用直截了当的逐层增长来准备光学透明的化学可寻址膜，该电影将用于固态光化学转换。该奖项反映了NSF的法定任务，并被认为是通过使用该基金会的知识分子和更广泛影响的评估来评估CRITERIA CRITERIA CRITERIA的评估。