Abstract
Inorganic–organic hybrid materials represent a large share of newly reported structures, owing to their simple synthetic routes and customizable properties1. This proliferation has led to a characterization bottleneck: many hybrid materials are obligate microcrystals with low symmetry and severe radiation sensitivity, interfering with the standard techniques of single-crystal X-ray diffraction2,3 and electron microdiffraction4–11. Here we demonstrate small-molecule serial femtosecond X-ray crystallography (smSFX) for the determination of material crystal structures from microcrystals. We subjected microcrystalline suspensions to X-ray free-electron laser radiation12,13 and obtained thousands of randomly oriented diffraction patterns. We determined unit cells by aggregating spot-finding results into high-resolution powder diffractograms. After indexing the sparse serial patterns by a graph theory approach14, the resulting datasets can be solved and refined using standard tools for single-crystal diffraction data15–17. We describe the ab initio structure solutions of mithrene (AgSePh)18–20, thiorene (AgSPh) and tethrene (AgTePh), of which the latter two were previously unknown structures. In thiorene, we identify a geometric change in the silver–silver bonding network that is linked to its divergent optoelectronic properties20. We demonstrate that smSFX can be applied as a general technique for structure determination of beam-sensitive microcrystalline materials at near-ambient temperature and pressure.
Highlights
Electron diffraction and powder X-ray diffraction (PXRD) are currently the dominant techniques for structural studies on microcrystals
SerialED uses a single-shot-per-crystal approach, with sample preparation methods that mirror those of MicroED, where microcrystals are in vacuum conditions and affixed to a substrate
Serial femtosecond crystallography (SFX) usually involves a liquid jet of many small crystals injected into the interaction point of an X-ray free-electron laser (XFEL)
Summary
XFEL smSFX can be used to solve structures of obligate microcrystals. We demonstrated this approach by using the cctbx.small_cell programme for indexing and integration of single-shot images from data collected on three microcrystalline materials. The resulting datasets were used to solve a 1.2-Å structure of mithrene, using a previous structure[19] only as a reference for method validation, and the 1.35-Å structures of thiorene and tethrene, with no reference structures This approach should be broadly applicable across XFELs and synchrotron radiation facilities equipped for serial crystallography. E. Automated electron diffraction tomography – a new tool for nano crystal structure analysis. Automated serial rotation electron diffraction combined with cluster analysis: an efficient multi-crystal workflow for structure determination. Serial electron crystallography for structure determination and phase analysis of nanocrystalline materials. Three-dimensional electron diffraction for structural analysis of beam-sensitive metal-organic frameworks. I. F. et al DASH: a program for crystal structure determination from powder diffraction data. Pattern-matching indexing of Laue and monochromatic serial crystallography data for applications in materials science. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
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