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Ligand-Mediated Quantum Yield Enhancement in 1-D Silver Organothiolate Metal–Organic Chalcogenolates

Aleksich, Mariya ; Cho, Yeongsu ; Paley, Daniel W. ; Willson, Maggie C. ; Nyiera, Hawi N. ; Kotei, Patience A. ; Oklejas, Vanessa ; Mittan-Moreau, David W. ; Schriber, Elyse A. and Christensen, Kara , et al. (2024) In Advanced Functional Materials
Abstract

X-ray free electron laser (XFEL) microcrystallography and synchrotron single-crystal crystallography are used to evaluate the role of organic substituent position on the optoelectronic properties of metal–organic chalcogenolates (MOChas). MOChas are crystalline 1D and 2D semiconducting hybrid materials that have varying optoelectronic properties depending on composition, topology, and structure. While MOChas have attracted much interest, small crystal sizes impede routine crystal structure determination. A series of constitutional isomers where the aryl thiol is functionalized by either methoxy or methyl ester are solved by small molecule serial femtosecond X-ray crystallography (smSFX) and single crystal rotational crystallography.... (More)

X-ray free electron laser (XFEL) microcrystallography and synchrotron single-crystal crystallography are used to evaluate the role of organic substituent position on the optoelectronic properties of metal–organic chalcogenolates (MOChas). MOChas are crystalline 1D and 2D semiconducting hybrid materials that have varying optoelectronic properties depending on composition, topology, and structure. While MOChas have attracted much interest, small crystal sizes impede routine crystal structure determination. A series of constitutional isomers where the aryl thiol is functionalized by either methoxy or methyl ester are solved by small molecule serial femtosecond X-ray crystallography (smSFX) and single crystal rotational crystallography. While all the methoxy examples have a low quantum yield (0-1%), the methyl ester in the ortho position yields a high quantum yield of 22%. The proximity of the oxygen atoms to the silver inorganic core correlates to a considerable enhancement of quantum yield. Four crystal structures are solved at a resolution range of 0.8–1.0 Å revealing a collapse of the 2D topology for functional groups in the 2- and 3- positions, resulting in needle-like crystals. Further analysis using density functional theory (DFT) and many-body perturbation theory (MBPT) enables the exploration of complex excitonic phenomena within easily prepared material systems.

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organization
publishing date
type
Contribution to journal
publication status
in press
subject
keywords
2D, MOChas, quantum yield
in
Advanced Functional Materials
publisher
Wiley-Blackwell
external identifiers
  • scopus:85210765949
ISSN
1616-301X
DOI
10.1002/adfm.202414914
language
English
LU publication?
yes
id
6cc10c6c-9ec2-41f5-926c-9df0910b77ca
date added to LUP
2025-01-21 15:54:27
date last changed
2025-04-04 14:45:35
@article{6cc10c6c-9ec2-41f5-926c-9df0910b77ca,
  abstract     = {{<p>X-ray free electron laser (XFEL) microcrystallography and synchrotron single-crystal crystallography are used to evaluate the role of organic substituent position on the optoelectronic properties of metal–organic chalcogenolates (MOChas). MOChas are crystalline 1D and 2D semiconducting hybrid materials that have varying optoelectronic properties depending on composition, topology, and structure. While MOChas have attracted much interest, small crystal sizes impede routine crystal structure determination. A series of constitutional isomers where the aryl thiol is functionalized by either methoxy or methyl ester are solved by small molecule serial femtosecond X-ray crystallography (smSFX) and single crystal rotational crystallography. While all the methoxy examples have a low quantum yield (0-1%), the methyl ester in the ortho position yields a high quantum yield of 22%. The proximity of the oxygen atoms to the silver inorganic core correlates to a considerable enhancement of quantum yield. Four crystal structures are solved at a resolution range of 0.8–1.0 Å revealing a collapse of the 2D topology for functional groups in the 2- and 3- positions, resulting in needle-like crystals. Further analysis using density functional theory (DFT) and many-body perturbation theory (MBPT) enables the exploration of complex excitonic phenomena within easily prepared material systems.</p>}},
  author       = {{Aleksich, Mariya and Cho, Yeongsu and Paley, Daniel W. and Willson, Maggie C. and Nyiera, Hawi N. and Kotei, Patience A. and Oklejas, Vanessa and Mittan-Moreau, David W. and Schriber, Elyse A. and Christensen, Kara and Inoue, Ichiro and Owada, Shigeki and Tono, Kensuke and Sugahara, Michihiro and Inaba-Inoue, Satomi and Vakili, Mohammad and Milne, Christopher J. and DallAntonia, 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 Macias, Ivette J.Bermudez 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 Mancuso, Adrian P. and Warren, Mark and Sauter, Nicholas K. and Zhao, Jing and Smidt, Tess and Kulik, Heather J. and Sharifzadeh, Sahar and Brewster, Aaron S. and Hohman, J. Nathan}},
  issn         = {{1616-301X}},
  keywords     = {{2D; MOChas; quantum yield}},
  language     = {{eng}},
  publisher    = {{Wiley-Blackwell}},
  series       = {{Advanced Functional Materials}},
  title        = {{Ligand-Mediated Quantum Yield Enhancement in 1-D Silver Organothiolate Metal–Organic Chalcogenolates}},
  url          = {{http://dx.doi.org/10.1002/adfm.202414914}},
  doi          = {{10.1002/adfm.202414914}},
  year         = {{2024}},
}