Chemical crystallography by serial femtosecond X-ray diffraction
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Abstract
<jats:title>Abstract</jats:title><jats:p>Inorganic–organic hybrid materials represent a large share of newly reported structures, owing to their simple synthetic routes and customizable properties<jats:sup>1</jats:sup>. 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 diffraction<jats:sup>2,3</jats:sup> and electron microdiffraction<jats:sup>4–11</jats:sup>. 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 radiation<jats:sup>12,13</jats:sup> 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 approach<jats:sup>14</jats:sup>, the resulting datasets can be solved and refined using standard tools for single-crystal diffraction data<jats:sup>15–17</jats:sup>. We describe the ab initio structure solutions of mithrene (AgSePh)<jats:sup>18–20</jats:sup>, 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 properties<jats:sup>20</jats:sup>. 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.</jats:p>