DOI: https://doi.org/10.29363/nanoge.dynamic.2023.007
Publication date: 15th February 2023
“Perfect crystals” are a human-made concept. Indeed, any crystalline material has some degree of aperiodicity in the form of defects, distortions, etc. In this regard, metal–organic frameworks (MOFs) are among the least periodic, most importantly due to their structure flexibility. Whether this manifests as static distortion or vibrations, characterizing the structural aspects of MOFs flexibility is a long-lasting challenge as conventional crystallography focuses on extracting from diffraction data only the average crystal structure. In this way, local deviations from idealised average models are systematically overlooked. While several complementary spectroscopy, imaging, or powder diffraction techniques provide valuable pieces of information on the complexity of real MOF structures, the use of diffuse scattering present in single crystal diffraction data can allow an actual determination of their 3D aperiodicity.1 Hereby, I will show how this technique afforded a detailed atomistic picture of the unexpectedly complex aperiodic structure of the MOF ZIF-90.2 A combination of Monte Carlo aperiodic crystal simulations and variable-temperature diffuse scattering analysis on single crystals revealed a hidden diversity of framework distortions involved in a temperature-induced phase transition. Our results shed light on a poorly known and uncontrolled degree of freedom in MOF chemistry with inspiring implications for the rational design of their aperiodicity, and highlighting the importance of a meticulous crystallographic inspection of disorder in framework structures.
Prof. Monique A. van der Veen and Prof. Omar M. Yaghi are gratefully thanked for upholding this collaborative work. The Research Fonudation Flanders (FWO) is acknowledged for finantial support (project nr. 12ZV120N).
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