Ashbrook Sharon E, Dawson Daniel M, Seymour Valerie R
School of Chemistry, EaStCHEM and St Andrews Centre for Magnetic Resonance, St Andrews KY16 9ST, UK.
Phys Chem Chem Phys. 2014 May 14;16(18):8223-42. doi: 10.1039/c4cp00578c.
Microporous materials, having pores and channels on the same size scale as small to medium molecules, have found many important applications in current technologies, including catalysis, gas separation and drug storage and delivery. Many of their properties and functions are related to their detailed local structure, such as the type and distribution of active sites within the pores, and the specific structures of these active sites. Solid-state NMR spectroscopy has a strong track record of providing the requisite detailed atomic-level insight into the structures of microporous materials, in addition to being able to probe dynamic processes occurring on timescales spanning many orders of magnitude (i.e., from s to ps). In this Perspective, we provide a brief review of some of the basic experimental approaches used in solid-state NMR spectroscopy of microporous materials, and then discuss some more recent advances in this field, particularly those applied to the study of crystalline materials such as zeolites and metal-organic frameworks. These advances include improved software for aiding spectral interpretation, the development of the NMR-crystallography approach to structure determination, new routes for the synthesis of isotopically-labelled materials, methods for the characterisation of host-guest interactions, and methodologies suitable for observing NMR spectra of paramagnetic microporous materials. Finally, we discuss possible future directions, which we believe will have the greatest impact on the field over the coming years.
微孔材料具有与小分子到中分子尺寸相当的孔和通道，在当前技术中已发现许多重要应用，包括催化、气体分离以及药物储存与递送。它们的许多性质和功能都与其详细的局部结构相关，例如孔内活性位点的类型和分布，以及这些活性位点的具体结构。固态核磁共振光谱除了能够探测跨越多个数量级时间尺度（即从秒到皮秒）上发生的动态过程外，在提供对微孔材料结构所需的详细原子水平洞察方面有着出色的记录。在这篇综述中，我们简要回顾了微孔材料固态核磁共振光谱中使用的一些基本实验方法，然后讨论该领域的一些最新进展，特别是那些应用于沸石和金属有机框架等晶体材料研究的进展。这些进展包括有助于光谱解释的改进软件、用于结构测定的核磁共振晶体学方法的发展、合成同位素标记材料的新途径、主客体相互作用的表征方法，以及适用于观测顺磁性微孔材料核磁共振谱的方法。最后，我们讨论了未来可能的发展方向，我们认为这些方向将在未来几年对该领域产生最大影响。
