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

非技术摘要：金属有机骨架材料因其在催化、提纯和分子存储等工业应用中的潜力而继续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化应用的障碍，其中一些骨架要么根本不形成，要么在尺度上降低了材料性能。虽然社区已经开发出几种合成这些材料的方法，但它们形成背后的基本化学仍有待阐明。这个项目的重点是了解MOF在组装早期阶段的形成机制，导致在合理设计、可扩展合成和提高工业相关性方面的进展。通过协同结合新材料的合成和利用光谱学，正在对MOF的形成有一个详细的了解。这种方法一直是包括制药业在内的其他合成领域的标志，在制药业，对机械有机化学的丰富了解直接导致了重磅炸弹药物的合成。为了提高成人的科学素养，在马宏宁山谷终身学习研究所(MVLLI)开始了一系列讲座，该研究所是一家以成人为中心的教育设施，重点是揭开材料化学的神秘面纱。技术摘要：研究活动集中于了解金属有机框架(MOF)建筑中无机二次建筑单元(SBU)的形成机理。这个项目概述了一个光谱和合成路线图，以获得对SBU的形成和随后的自组装过程的机械理解。这一水平的理解预计将导致更有效地合成MOF，并产生具有以前无法获得的无数属性的新颖框架架构。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(目标1)。确定的中间体然后以分子形式或聚合物形式用于独立合成(目标2)。对合成的中间体进行进一步的化学处理，得到传统方法无法实现的电子多样性的共聚物(目标3)。本科生和硕士学生参与了这个项目的方方面面，从MOF的合成和光谱学到为成人外展计划做演讲。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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.