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

RUI：通过串联光谱和合成方法阐明金属有机框架中次级建筑单元形成的机制。

基本信息

批准号：
1807462
负责人：
Douglas Genna
金额：
$ 29.39万
依托单位：
Youngstown State University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-09-01 至 2023-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1807462&HistoricalAwards=false
关键词：
RUI Mechanistic Elucidation Formation Secondary

项目摘要

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.

非技术摘要：金属有机框架 (MOF) 因其在催化、纯化和分子存储等工业应用中的潜力而不断引起材料研究界的兴趣。 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，要么在扩展时材料性能降低。尽管业界已经开发了多种合成这些材料的方法，但其形成背后的基本化学仍有待阐明。该项目的重点是了解 MOF 在组装早期阶段的形成机制，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，人们正在深入了解 MOF 的形成。这种方法是包括制药行业在内的其他合成领域的标志，在制药行业中，对机械有机化学的丰富理解直接导致了重磅药物的合成。为了提高成人的科学素养，马哈宁谷终身学习学院 (MVLLI) 启动了一系列讲座，这是一个以成人为中心的教育机构，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）结构中无机二次结构单元（SBU）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械理解。这种水平的理解预计将导致更有效的 MOF 合成，并产生具有以前无法获得的未知特性的新颖框架架构。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）。然后将确定的中间体以分子或聚合形式进行独立合成（目标 2）。合成的中间体经过进一步的化学处理，产生传统方法无法实现的电子多样化的共聚物（目标 3）。本科生和硕士水平的学生参与了该项目的各个方面，从 MOF 合成和光谱学到为成人外展计划提供讲座。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进行评估，被认为值得支持审查标准。

项目成果

期刊论文数量（4）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Mechanistic Investigation of the Synthesis of Dianionic In-Derived Coordination Polymers

双阴离子衍生配位聚合物的合成机理研究

DOI：
10.1021/acs.inorgchem.3c00148
发表时间：
2023-04
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Tatebe, Caleb J.;Fromel, Emily;Bellas, Michael K.;Zeller, Matthias;Genna, Douglas T.
通讯作者：
Genna, Douglas T.

Framework Isomerism in a Series of btb-Containing In-Derived Metal–Organic Frameworks

一系列含 btb 衍生金属有机骨架中的骨架异构现象

DOI：
10.1021/acs.cgd.9b00611
发表时间：
2019-05-15
期刊：
Crystal Growth & Design
影响因子：
3.8
作者：
S. E. Springer;Joseph J. Mihaly;Naseem Amirmokhtari;Audrey B. Crom;M. Zeller;Jeremy I. Feldblyum;D. Genna
通讯作者：
D. Genna

On the Role of Dioxane in the Synthesis of In-Derived MOFs

二恶烷在衍生 MOF 合成中的作用

DOI：
10.1021/acs.cgd.1c00766.s001
发表时间：
2021-11-11
期刊：
Crystal Growth & Design
影响因子：
3.8
作者：
Caleb J. Tatebe;Saidah Yusuf;M. Bellas;M. Zeller;C. Arntsen;D. Genna
通讯作者：
D. Genna

Halide Directed Synthesis of an In-Derived Metal–Organic Framework with Two Unique Metal Centers and Isolation of Its Potential Synthetic Precursor

具有两个独特金属中心的衍生金属有机框架的卤化物定向合成及其潜在合成前体的分离

DOI：
10.1021/acs.cgd.9b01301
发表时间：
2019-10-16
期刊：
Crystal Growth & Design
影响因子：
3.8
作者：
Joseph J. Mihaly;Caleb J. Tatebe;Naseem Amirmokhtari;Marisa J. DeSanto;M. Zeller;D. Genna
通讯作者：
D. Genna