Insights from Nuclear Magnetic Resonance into Bonding Interactions in Solids

核磁共振（NMR）光谱是研究所有形式物质的首要非破坏性分析方法。我们的研究计划专注于NMR光谱方法的开发和应用，重点是提供对固体结构和键合的见解。我们还应用计算化学来补充我们的实验结果。 我们的目标是为几个具有广泛兴趣的领域做出新颖的创新贡献。需要处理的三个具体方向是： (i)非共价相互作用的NMR参数的统一描述。我们将系统地探索广泛的非共价相互作用，目的是对键合环境和强度之间的关系以及观察到的NMR参数提供统一的理解。例如，最近在理解SN 2亲核取代反应的上下文中强调了四元键，其中第14族元素如碳充当亲电体。我们将通过多核固态磁共振光谱制备和表征参与周期表中元素之间形成的非共价键的亲电和亲核试剂。这项工作将提供非常独特的实验见解非共价键，这是关键的结构，键合和材料，超分子化学和生物分子的反应性。 (ii)通过核磁共振光谱对金属-金属键合的新见解。我们将开发和应用多核和多维核磁共振方法来直接探测固体中的金属-金属键合相互作用。由于许多感兴趣的金属同位素的强四极性质，这长期以来一直是一个艰巨的挑战。这项工作将为金属-金属键合的性质提供新的见解，并将解决对催化和石化工业具有重要意义的金属有机框架（MOFs）中的金属-金属相互作用。这项工作有很强的潜力，导致一个敏感和独特的探针的对称性和吸附的MOFs，具有不同的应用跨学科。 (iii)最后一个新的研究方向包括一个仲氢流系统的发展和应用，以hyperhammerlow-receptivity核在固体中。这项高风险的工作有望将我们对键合相互作用的研究提升到一个新的水平，使其适用于“真实的”样品的低成本研究，例如在表面或多相催化剂中发现的样品。

Nuclear magnetic resonance (NMR) spectroscopy is the premier non-destructive analytical method for studying all forms of matter. Our research program is focussed on the development and application of NMR spectroscopic methods with an emphasis on providing insights into structure and bonding in solids. We also apply computational chemistry to complement our experimental results. We aim to make novel innovative contributions to several areas of broad interest. Three specific directions to be addressed are: (i) A unified description of non-covalent interactions in terms of NMR parameters. We will systematically explore a broad range of non-covalent interactions with the goal of providing a unified understanding of the relationship between the bonding environment and strength, and the observed NMR parameters. For example, the tetrel bond, in which group 14 elements such as carbon act as electrophiles, has recently been highlighted in the context of understanding the SN2 nucleophilic substitution reaction. We will prepare and characterize via multinuclear solid-state magnetic resonance spectroscopy the electrophiles and nucleophiles involved in non-covalent bonds formed between elements from across the periodic table. This work will provide highly unique experimental insights into non-covalent bonds which are key to structure, bonding, and reactivity in materials, supramolecular chemistry, and biomolecules. (ii) New insights into metal-metal bonding via NMR spectroscopy. We will develop and apply multinuclear and multidimensional NMR methods to directly probe metal-metal bonding interactions in solids. This has long represented a daunting challenge because of the strong quadrupolar nature of many metal isotopes of interest. This work will provide novel insight into the nature of metal-metal bonding and will also address metal-metal interactions in metal-organic frameworks (MOFs) of importance to catalysis and the petrochemical industry. This work has strong potential to lead to a sensitive and unique probe of symmetry and adsorption in MOFs, with diverse applications across disciplines. (iii) A final novel research direction consists of the development and application of a parahydrogen flow system to hyperpolarize low-receptivity nuclei in solids. This high-risk work promises to take our studies of bonding interactions to the next level, rendering them applicable to the low-cost study of ‘real’ samples such as those found on surfaces or in heterogeneous catalysts.