We study the metal-organic framework (MOF) ZIF-67 with ¹H and ¹³C nuclear magnetic resonance (NMR). In addition to the usual orbital chemical shifts, we observe spinning sideband manifolds in the NMR spectrum due to hyperfine interactions of the paramagnetic cobalt with ¹H and ¹³C. Both orbital and paramagnetic chemical shifts are in good agreement with values calculated from first principles, allowing high-confidence assignment of the observed peaks to specific sites within the MOF. Our measured resonance shifts, line shapes, and spin lattice relaxation rates are also consistent with calculated values. We show that molecules in the pores of the MOF can exhibit high-resolution NMR spectra with fast spin lattice relaxation rates due to dipole-dipole couplings to the Co²⁺ nodes in the ZIF-67 lattice, showcasing NMR spectroscopy as a powerful tool for identification and characterization of “guests” that may be hosted by the MOF in electrochemical and catalytic applications.

^{我们使用1} H 和¹³ C 核磁共振 (NMR)研究金属有机框架 (MOF) ZIF-67 。除了通常的轨道化学位移外，我们还观察到 NMR 光谱中的自旋边带流形，这是由于顺磁性钴与¹ H 和¹³C. 轨道和顺磁性化学位移都与根据第一原理计算的值非常一致，允许将观察到的峰高度可靠地分配到 MOF 内的特定位置。我们测量的共振位移、线形和自旋晶格弛豫率也与计算值一致。^{我们表明，由于偶极-偶极耦合到 ZIF-67 晶格中的 Co 2+}节点， MOF 孔隙中的分子可以表现出具有快速自旋晶格弛豫速率的高分辨率 NMR 光谱，展示了 NMR 光谱作为一种强大的工具在电化学和催化应用中可能由 MOF 承载的“客体”的识别和表征。