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

• 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

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，特拉华大学的Eric Bloch和德克萨斯农工大学的David Powers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应用，包括水过滤和/或软化、作为干燥剂和医药。 多孔材料的一个子集被大规模用于催化应用，包括碳氢化合物的裂解。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决定其活性方面发挥作用。 Bloch/Powers 团队正在以有希望的初步结果为基础，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。在该方法中，带电的无孔反应性有机金属物质将与带相反电荷的多孔非反应性离子结合，形成新型多孔固体。 可以预见，对于如此构建的多孔材料，催化活性将在一系列有用的转化中进行精细调节，包括碳-氢键官能化和交叉偶联反应。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来表征催化转化过程中的活性物质。博士。布洛赫和鲍尔斯将继续致力于增加科学的多样性，通过当地和区域教育经验，包括为本科生和研究生开发一所年度 X 射线粉末衍射在线学校，将合成化学研究的乐趣带给广大受众。该合作项目的目标是开发用于位点隔离和固态有机金属化学的新型多孔材料。虽然设计的多孔固体（例如沸石和金属有机框架）作为多相催化剂显示出了令人难以置信的前景，但在有限空间内开发固态有机金属化学的通用平台仍然难以捉摸。这项工作旨在将带电的永久多孔配位笼与带互补电荷的反应性有机金属片段结合起来，以制备一类新型反应性催化剂——多孔盐。在本次资助期间，布洛赫和鲍尔斯将阐明多孔盐的一般结构功能特性，其中笼电荷、几何形状和官能团呈现将用于调整盐结构和孔隙率。随后，布洛赫和鲍尔斯将使用这些盐作为平台，将设计者的反应离子融入多孔固体中，在多孔固体中研究小分子结合和活化，以评估盐的活性。要研究的反应包括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，用于固态光化学转化。该奖项反映了NSF的法定使命，并通过评估被认为值得支持利用基金会的智力优势和更广泛的影响审查标准。

项目成果

Porous Salts as Platforms for Heterogeneous Catalysis

多孔盐作为多相催化平台

• DOI: 10.1002/smll.202207507
• 发表时间: 2023-04
• 期刊: Small
• 影响因子: 13.3
• 作者: Korman, Kyle J.;Dworzak, Michael R.;Yap, Glenn P. A.;Bloch, Eric D.
• 通讯作者: Bloch, Eric D.

Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films

利用光学透明的多孔盐薄膜解锁固态有机金属光化学

• DOI: 10.1021/jacs.3c09188
• 发表时间: 2023-11-08
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Aishanee Sur;Joe D Simmons;Andrew A. Ezazi;Kyle J. Korman;Subham Sarkar;Ethan T. Iverson;Eric D. Bloch;D. Powers
• 通讯作者: D. Powers