Ligand‐Mediated Quantum Yield Enhancement in 1‐D Silver Organothiolate Metal–Organic Chalcogenolates
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. 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.
Authors
- O. Turkot (ORCID: https://orcid.org/0000-0001-5352-7744)
- Aaron S. Brewster (ORCID: https://orcid.org/0000-0002-0908-7822)
- Patience A. Kotei (ORCID: https://orcid.org/0000-0001-6002-1645)
- Fabio Dall’Antonia
- Philipp Schmidt (ORCID: https://orcid.org/0000-0003-1980-6998)
- Hazem Yousef (ORCID: https://orcid.org/0009-0000-7344-2529)
- Luca Gelisio (ORCID: https://orcid.org/0000-0001-7832-6201)
- Kirsten E. Christensen (ORCID: https://orcid.org/0000-0003-1683-2066)
- Fernando Ardana‐Lamas (ORCID: https://orcid.org/0000-0001-9028-5051)
- Mohammad Vakili (ORCID: https://orcid.org/0000-0001-9776-0177)
- Joana Valério (ORCID: https://orcid.org/0000-0001-5931-0925)
- Huijong Han (ORCID: https://orcid.org/0000-0002-1197-3014)
- Ichiro Inoue (ORCID: https://orcid.org/0009-0008-0423-1347)
- J. Nathan Hohman (ORCID: https://orcid.org/0000-0002-9777-6432)
- Mark R. Warren (ORCID: https://orcid.org/0000-0003-1326-0744)
- Dmitry Khakhulin (ORCID: https://orcid.org/0000-0002-4453-1204)
- Thomas Kluyver (ORCID: https://orcid.org/0000-0003-4020-6364)
- Satomi Inaba‐Inoue (ORCID: https://orcid.org/0000-0002-6939-1324)
- Adrian P. Mancuso⋈ (ORCID: https://orcid.org/0000-0003-1710-8969)
- Doriana Vinci (ORCID: https://orcid.org/0000-0001-8841-6534)
- Yifeng Jiang (ORCID: https://orcid.org/0000-0003-0685-0498)
- Sahar Sharifzadeh (ORCID: https://orcid.org/0000-0003-4215-4668)
- Ivette J. Bermúdez Macias (ORCID: https://orcid.org/0000-0002-2842-4230)
- Heather Janine Kulik (ORCID: https://orcid.org/0000-0001-9342-0191)
- Kensuke Tono (ORCID: https://orcid.org/0000-0003-1218-3759)
- Vanessa Oklejas (ORCID: https://orcid.org/0000-0001-5696-4720)
- Shigeki Owada (ORCID: https://orcid.org/0000-0002-1451-7612)
- Michihiro Sugahara
- Tess Smidt (ORCID: https://orcid.org/0000-0001-5581-5344)
- Adam Round (ORCID: https://orcid.org/0000-0002-0723-8228)
- David Moreau (ORCID: https://orcid.org/0000-0002-3193-571X)
- Nicholas K. Sauter (ORCID: https://orcid.org/0000-0003-2786-6552)
- Elyse A. Schriber⧓ (ORCID: https://orcid.org/0000-0002-8935-2955)
- Frederico A. Lima (ORCID: https://orcid.org/0000-0001-8106-2892)
- Yeongsu Cho (ORCID: https://orcid.org/0000-0001-8159-600X)
- Yohei Uemura (ORCID: https://orcid.org/0000-0003-3164-7168)
- Jing Zhao (ORCID: https://orcid.org/0000-0002-6882-2196)
- Hawi N. Nyiera (ORCID: https://orcid.org/0009-0002-2707-052X)
- Daniel W. Paley⧓ (ORCID: https://orcid.org/0000-0003-1161-5142)
- Marco Kloos (ORCID: https://orcid.org/0000-0002-8745-9740)
- Tamires Gallo (ORCID: https://orcid.org/0000-0003-3844-0872)
- Christopher J. Milne (ORCID: https://orcid.org/0000-0003-4714-9139)
- Mariya Aleksich⧓ (ORCID: https://orcid.org/0009-0004-2251-6013)
- Maggie C. Willson (ORCID: https://orcid.org/0009-0003-0188-1735)
Institutions
- Boston University (US)
- University of Connecticut (US)
- Lawrence Berkeley National Laboratory (US)
- Universität Hamburg (DE)
- Lund University (SE)
- La Trobe University (AU)
- Hokkaido University (JP)
- Deutsches Elektronen-Synchrotron DESY (DE)
- SLAC National Accelerator Laboratory (US)
- Diamond Light Source (GB)
- SPring-8 (JP)
- Japan Synchrotron Radiation Research Institute (JP)
- MAX IV Laboratory (SE)
- Linac Coherent Light Source (US)
- Center for Free-Electron Laser Science (DE)
- Massachusetts Institute of Technology (US)
- European X-Ray Free-Electron Laser (DE)
Publication Details
- Journal
- Advanced Functional Materials
- Published
- 2024-12-01
- DOI
- https://doi.org/10.1002/adfm.202414914
- Citations
- 9
- Primary Topic
- Perovskite Materials and Applications
- Type
- article
- Field-Weighted Citation Impact
- 1.88
Funders
- National Science Foundation
- U.S. Department of Energy
- Office of Science
- Basic Energy Sciences