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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.

在化学系化学合成项目的支持下，特拉华州大学的Eric Bloch和德克萨斯A M大学的大卫鲍尔斯将研究制备多孔催化剂的新方法。多孔材料在世界各地广泛用于各种各样的应用，包括水过滤和/或软化、作为干燥剂以及用于医学。多孔材料的子集大规模地用于催化应用，包括烃的裂化。然而，使用多孔材料作为催化剂的一个关键挑战是控制和优化其反应性，其中总表面积，结构类型和稳定性可以在确定其活性方面发挥作用。Bloch/Powers团队正在建立有希望的初步结果，以开发一种通过产生反应性盐来合成活性多孔催化剂的新方法。在这种方法中，带电的非多孔活性有机金属物种将与带相反电荷的多孔非活性离子结合，以提供一类新的多孔固体。可以设想，对于如此构造的多孔材料，催化活性将在包括碳-氢键官能化和交叉偶联反应在内的一系列有用的转化中精细地可调。除此之外，这些研究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活性物质。Bloch博士和Powers博士将继续致力于增加科学的多样性，通过当地和地区的教育经验，将合成化学研究的兴奋带给广大观众，包括为本科生和研究生开发年度X射线粉末衍射在线学校。这个合作项目的目标是开发用于现场隔离和固态有机金属化学的新型多孔材料。虽然设计师多孔固体，如沸石和金属有机框架已显示出令人难以置信的承诺作为非均相催化剂，一般的平台，用于发展的固态有机金属化学在有限的空间仍然难以捉摸。本工作旨在将联合收割机带电的、永久多孔的配位笼与互补带电的反应性有机金属片段相结合，用于制备一类新的反应性催化剂，多孔盐。在此资助期间，Bloch和Powers将阐明多孔盐的一般结构-功能特性，其中笼状电荷，几何形状和官能团介绍将被用来调整盐结构和孔隙率。随后，Bloch和Powers将使用这些盐作为平台，将设计者反应离子结合到多孔固体中，研究小分子结合和活化以评估盐的活性。待研究的反应将包括C-H键官能化和交叉偶联催化。最后，Bloch/Powers团队将利用简单的逐层生长来制备光学透明、化学可寻址的薄膜，这些薄膜将用于固态光化学转换。该奖项反映了NSF的法定使命，并被认为值得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来支持。