학술논문
XFEL Microcrystallography of Self-Assembling Silver n-Alkanethiolates
Document Type
Author
Aleksich, Mariya; Paley, Daniel W.; Schriber, Elyse A.; Linthicum, Will; Oklejas, Vanessa; Mittan-Moreau, David W.; Kelly, Ryan P.; Kotei, Patience A.; Ghodsi, Anita; Sierra, Raymond G.; Aquila, Andrew; Poitevin, Frédéric; Blaschke, Johannes P.; Vakili, Mohammad; Milne, Christopher J.; Dall’Antonia, Fabio; Khakhulin, Dmitry; Ardana-Lamas, Fernando; Lima, Frederico; Valerio, Joana; Han, Huijong; Gallo, Tamires; Yousef, Hazem; Turkot, Oleksii; Bermudez Macias, Ivette J.; Kluyver, Thomas; Schmidt, Philipp; Gelisio, Luca; Round, Adam R.; Jiang, Yifeng; Vinci, Doriana; Uemura, Yohei; Kloos, Marco; Hunter, Mark; Mancuso, Adrian P.; Huey, Bryan D.; Parent, Lucas R.; Sauter, Nicholas K.; Brewster, Aaron S.; Hohman, J. Nathan
Source
Journal of the American Chemical Society. 145(31):17042-17055
Subject
Language
English
ISSN
0002-7863
Abstract
New synthetic hybrid materials and their increasing complexity have placed growing demands on crystal growth for single-crystal X-ray diffraction analysis. Unfortunately, not all chemical systems are conducive to the isolation of single crystals for traditional characterization. Here, small-molecule serial femtosecond crystallography (smSFX) at atomic resolution (0.833 Å) is employed to characterize microcrystalline silver n-alkanethiolates with various alkyl chain lengths at X-ray free electron laser facilities, resolving long-standing controversies regarding the atomic connectivity and odd-even effects of layer stacking. smSFX provides high-quality crystal structures directly from the powder of the true unknowns, a capability that is particularly useful for systems having notoriously small or defective crystals. We present crystal structures of silver n-butanethiolate (C4), silver n-hexanethiolate (C6), and silver n-nonanethiolate (C9). We show that an odd-even effect originates from the orientation of the terminal methyl group and its role in packing efficiency. We also propose a secondary odd-even effect involving multiple mosaic blocks in the crystals containing even-numbered chains, identified by selected-area electron diffraction measurements. We conclude with a discussion of the merits of the synthetic preparation for the preparation of microdiffraction specimens and compare the long-range order in these crystals to that of self-assembled monolayers.