Multi‐Crystal X‐Ray Diffraction (MCXRD) Bridges the Crystallographic Characterisation Gap in Chemistry and Materials Science: Application to MOFs

Abstract Structure determination by X‐ray diffraction is limited by crystal size and can be compromised by radiation damage when using very intense X‐ray radiation. X‐ray structure determination from partial diffraction data sets combined from multiple crystals is a potential solution, but its exploitation in chemistry and materials science is largely unrealized. Here we report the use of synchrotron radiation for multi‐crystal X‐ray diffraction (MCXRD) adapted for structure determination of metal‐organic framework (MOF) materials with crystal dimensions too small for conventional single‐crystal diffraction studies. We further show that radiation‐induced chemical changes and degradation of diffraction quality can be alleviated. Our approach encompasses both rotation‐ and stationary‐MCXRD measurements for 10 to 1000s of crystals with software‐optimized combination of the multiple data sets. We report the crystal structures of six MOFs: MOF‐919(Sc/Cu), MET‐2, MIL‐88B(Cr)‐1,4‐NDC, PCN‐260(Sc), UiO‐66, and UiO‐66‐MoO 4 with unit cell dimensions ranging from 18−114 Å and crystal sizes from 0.5−480 µm 3 . This approach can address the challenges of structure determination in a regime of particle size and sample radiation sensitivity that lies between existing single‐crystal X‐ray diffraction and the emerging field of electron diffraction. MCXRD can provide accurate atomic‐resolution structure determination for some of the most challenging cases in chemistry and materials science.