XFEL Microcrystallography of Self-Assembling Silver n-Alkanethiolates
(2023) In Journal of the American Chemical Society 145(31). p.17042-17055- 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... (More)
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.
(Less)
- author
- organization
- publishing date
- 2023-08-09
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of the American Chemical Society
- volume
- 145
- issue
- 31
- pages
- 14 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:37524069
- scopus:85167480510
- ISSN
- 0002-7863
- DOI
- 10.1021/jacs.3c02183
- language
- English
- LU publication?
- yes
- id
- f68a092e-e605-4ac7-9b88-c639f1cf65da
- date added to LUP
- 2023-12-19 16:20:00
- date last changed
- 2024-04-18 02:27:01
@article{f68a092e-e605-4ac7-9b88-c639f1cf65da,
abstract = {{<p>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.</p>}},
author = {{Aleksich, Mariya and Paley, Daniel W. and Schriber, Elyse A. and Linthicum, Will and Oklejas, Vanessa and Mittan-Moreau, David W. and Kelly, Ryan P. and Kotei, Patience A. and Ghodsi, Anita and Sierra, Raymond G. and Aquila, Andrew and Poitevin, Frédéric and Blaschke, Johannes P. and Vakili, Mohammad and Milne, Christopher J. and Dall’Antonia, Fabio and Khakhulin, Dmitry and Ardana-Lamas, Fernando and Lima, Frederico and Valerio, Joana and Han, Huijong and Gallo, Tamires and Yousef, Hazem and Turkot, Oleksii and Bermudez Macias, Ivette J. and Kluyver, Thomas and Schmidt, Philipp and Gelisio, Luca and Round, Adam R. and Jiang, Yifeng and Vinci, Doriana and Uemura, Yohei and Kloos, Marco and Hunter, Mark and Mancuso, Adrian P. and Huey, Bryan D. and Parent, Lucas R. and Sauter, Nicholas K. and Brewster, Aaron S. and Hohman, J. Nathan}},
issn = {{0002-7863}},
language = {{eng}},
month = {{08}},
number = {{31}},
pages = {{17042--17055}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Journal of the American Chemical Society}},
title = {{XFEL Microcrystallography of Self-Assembling Silver n-Alkanethiolates}},
url = {{http://dx.doi.org/10.1021/jacs.3c02183}},
doi = {{10.1021/jacs.3c02183}},
volume = {{145}},
year = {{2023}},
}