CAREER: Small Molecule Redox Reactivity at MOF Secondary Building Units

非技术摘要这个项目描述了一个职业计划，它结合了氧化还原活性金属-有机框架材料小分子反应性的基础研究，创建了交互式无机化学课程材料，供全球数百万学生使用，并努力增加波士顿市中心学校高中生的大学申请。本项目中合成和研究的材料和小分子底物代表了一大类世界关注的新兴材料，称为金属有机骨架(MOF)，以及与生物学和化学工业有关的小分子。技术摘要这项研究解决了自然界和合成化学家利用与生物和工业催化有关的小分子的方法之间的明显脱节。虽然生命系统使用复杂的超分子结构，其中多种因素-折叠、活性中心环境、次级球相互作用-有助于底物的选择性和整体反应，但使用小分子作为底物的金属络合物通常依赖于几乎完全集中在初级配位球上的配体设计，并且往往达不到自然界中看到的功能。研究小组已经证明，微孔MOF在配位场环境中支持高度还原的第一排过渡金属离子，这种环境模仿了在自然系统中发现的那些。这些离子与小分子氧化剂相互作用的方式也让人想起生物和工业催化循环中涉及的活性中间体。该团队的工作突出了这些材料可以作为非均质材料发挥的独特作用，它填补了金属酶和沸石等多孔非均质材料之间缺失的重要一环。该项目专注于合成能够与小分子结合进一步进行反应的新型氧化还原活性多孔材料，追求三个主要方向：(1)合成和表征具有高氧化还原活性的金属离子的MOF，包括许多尚未在此类材料中分离出来的金属离子；(2)探索新骨架的氧化还原活性，特别是关注工业上具有工业意义的气态氧化剂，如二氧化碳和卤素；(3)开发新的、可预测的软合成方法，以制备具有氧化还原活性的金属中心的MOF，以及用于MOF中小分子氧化还原化学的新的合成工具箱。

Non-technical abstractThis project describes a career plan that integrates fundamental studies of small molecule reactivity at redox-active metal-organic framework materials with the creation of interactive inorganic chemistry course materials to be made available to millions of students worldwide and with efforts to increase college applications from high school students in inner-city Boston schools. The materials and small molecule substrates synthesized and studied in this project are representative of large classes of emerging materials of worldwide interest known as metal-organic frameworks (MOFs) and of small molecules relevant in both biology and the chemical industry. Technical abstractThis research addresses the apparent disconnect between the ways Nature and synthetic chemists approach the utilization of small molecules of relevance to biological and industrial catalysis. While living systems use complex supramolecular architectures where multiple factors - folding, active site environment, secondary sphere interactions - contribute to substrate selectivity and overall reactivity, metal complexes that use small molecules as substrates typically rely on ligand design that focuses almost entirely on the primary coordination sphere, and often fall short of the functionality seen in Nature. The research team has shown that microporous MOFs support highly reduced first row transition metal ions in ligand field environments that mimic those found in natural systems. These ions interact with small molecule oxidants in ways that are also reminiscent of reactive intermediates involved in both biological and industrial catalytic cycles. The team's work highlights the unique role that these materials could play as heterogeneous materials by filling an important missing link between metalloenzymes and porous heterogeneous materials such as zeolites. The project focuses on synthesizing new redox-active porous materials capable of engaging small molecules for further reactivity, pursing three main directions: (1) The synthesis and characterization of MOFs with highly redox-active and reduced metal ions, including many that have not yet been isolated within such materials; (2) Exploration of the redox reactivity of the new frameworks, focusing in particular on small, industrially relevant gaseous oxidants such as dioxygen and the halogens; (3) Developing new and predictable soft synthetic methodologies for producing MOFs with redox-active metal centers and a new synthetic toolbox for small molecule redox chemistry in MOFs.