RUI: Mechanistic Elucidation of the Formation of Secondary Building Units in Metal Organic Frameworks via Tandem Spectroscopic and Synthetic Approaches.

摘要：金属有机框架（mof）由于其在催化、纯化和分子存储等工业应用方面的潜力而不断受到材料研究界的关注。MOF合成的可扩展性一直是大规模工业实施的障碍，其中一些框架要么根本不形成，要么在缩放时材料性能降低。虽然学界已经开发了几种合成这些材料的方法，但它们形成背后的基本化学原理仍有待阐明。该项目的重点是在组装的早期阶段了解MOF的形成机制，从而在合理设计、可扩展合成和提高工业相关性方面取得进展。通过协同结合新材料的合成和利用光谱学，对MOF的形成有了详细的了解。这种方法已经成为其他合成领域的标志，包括制药工业，其中对机械有机化学的丰富理解直接导致了重磅药物的合成。为了提高成年人的科学素养，以成人为中心的教育机构——马洪宁山谷终身学习研究所（MVLLI）开展了一系列讲座，重点是揭开材料化学的神秘面纱。技术摘要：研究活动的重点是了解金属有机框架（MOF）建筑中无机二级建筑单元（SBUs）的形成机制。该项目概述了光谱和合成路线图，以获得对SBU形成和随后的自组装过程的机理理解。这种水平的理解有望导致更有效的mof合成和具有以前无法获得的未知属性的新框架体系结构。拉曼光谱用于在完全形成的MOF沉淀之前识别溶液相中间体（目的1）。鉴定的中间体然后以分子或聚合物形式进行独立合成（目标2）。合成的中间体经过进一步的化学反应，产生电子多样化的共聚物，这是传统方法无法实现的（目标3）。本科和硕士水平的学生参与这个项目的各个方面，从MOF合成和光谱学到为成人拓展计划提供讲座。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。

Non-Technical Abstract:Metal-organic frameworks (MOFs) are materials that continue to gain interest from the materials research community for their potential in industrial applications such as catalysis, purification, and molecular storage. The scalability of MOF syntheses has always been a barrier to large scale industrial implementation, in which some frameworks either do not form at all or have diminished materials properties upon scaling. While the community has developed several methods for the synthesis of these materials, the fundamental chemistry behind their formation remains to be elucidated. This project focuses on understanding the mechanism of MOF formation at the early stages of their assembly, leading to advances in rational design, scalable synthesis, and increased industrial relevance. Through synergistically combining the synthesis of new materials and utilizing spectroscopy a detailed understanding of MOF formation is being developed. Such approaches have been the hallmark of other synthetic fields including the pharmaceutical industry in which a rich understanding of mechanistic organic chemistry has directly led to the synthesis of blockbuster drugs. To increase adult scientific literacy, a lecture series at the Mahoning Valley Lifelong Learning Institute (MVLLI), an adult-centered education facility, focusing on demystifying materials chemistry has been initiated. Technical Abstract:The research activities focus on understanding the mechanism of formation of the inorganic secondary building units (SBUs) in metal-organic framework (MOF) architectures. This project outlines a spectroscopic and synthetic road map to gain mechanistic understanding of the formation of the SBU and the subsequent self-assembly process. This level of understanding is expected to lead to more efficient syntheses of MOFs and to novel framework architectures with untold properties that were previously inaccessible. Raman spectroscopy is used to identify solution-phase intermediates prior to the precipitation of the fully formed MOF (Objective 1). The identified intermediates are then targeted for independent synthesis in either molecular or polymeric form (Objective 2). The synthesized intermediates are subjected to further chemistry which yields electronically diverse copolymers that cannot be realized by traditional means (Objective 3). Undergraduate and Master level students are involved in all aspects of this project from MOF syntheses and spectroscopy to delivering lectures for the adult outreach program.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.