Nucleophilic Displacement Reactions of Silver-Based Metal–Organic Chalcogenolates

Fan, Qiaoling; Willson, Maggie C.; Foell, Kristen A.; Paley, Daniel W.; Kotei, Patience A.; Schriber, Elyse A.; Rosenberg, Daniel J.; Rani, Komal; Tchoń, Daniel M.; Zeller, Matthias; Melendrez, Cynthia; Kang, Jungmin; Inoue, Ichiro; Owada, Shigeki; Tono, Kensuke; Sugahara, Michihiro; Brewster, Aaron S.; Hohman, J. Nathan

doi:10.1021/jacs.4c10426

Nucleophilic Displacement Reactions of Silver-Based Metal–Organic Chalcogenolates

Journal Article · Wed Oct 23 00:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c10426· OSTI ID:2575243

Fan, Qiaoling ^[1]; ^[1]; Foell, Kristen A. ^[1]; Paley, Daniel W. ^[2]; ^[1]; Schriber, Elyse A. ^[3]; Rosenberg, Daniel J. ^[3]; Rani, Komal ^[1]; ^[2]; ^[4]; Melendrez, Cynthia ^[3]; ^[5]; Inoue, Ichiro ^[5]; Owada, Shigeki ^[6]; Tono, Kensuke ^[6]; Sugahara, Michihiro ^[5]; ^[2]; ^[1]

Univ. of Connecticut, Storrs, CT (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
Purdue Univ., West Lafayette, IN (United States)
RIKEN SPring-8 Center, Sayo (Japan)
RIKEN SPring-8 Center, Sayo (Japan); Japan Synchrotron Radiation Research Institute, Sayo, Hyogo (Japan)

Here, we report nucleophilic displacement reactions that can increase the dimensionality or coordination number of silver-based metal–organic chalcogenolates (MOChas). MOChas are crystalline ensembles containing one-dimensional (1D) or two-dimensional (2D) inorganic topologies with structures and properties defined by the choice of metal, chalcogen, and ligand. MOChas can be readily prepared from a variety of small-molecule ligands and metals or metal ions. Although MOChas offer ligand diversity, most reported examples use relatively small ligands, typically involving short alkyl chains, aryl rings, or molecular cages. This is because larger, more complex molecules often yield poor product morphologies with indeterminate structures. In this study, we overcame this limitation by employing a ligand exchange strategy whereby a 1D MOCha, silver(I) methyl 2-mercaptobenzoate (2MMB), is used as a silver source for preparing 2D examples. The reaction proceeds generally toward products composed of the stronger nucleophile. We show that the reaction prefers displacing 1D topologies to yield 2D ones and replacing thiolates with selenolates. We performed a study to characterize the mechanism by which organic chalcogenols and dichalcogenides exchange with MOChas. The collected data and product analysis support a proposed mechanism of nucleophilic substitution, explaining how both organic chalcogenols and dichalcogenides can displace ligands in MOChas. This work provides a new synthetic route that will enable the preparation of more elaborate MOChas and heterostructures thereof. This approach enabled the preparation of previously inaccessible oligophenyl MOChas, which were successfully solved via small-molecule serial femtosecond crystallography (smSFX) at the SPring-8 Ångström Compact Free Electron LAser (SACLA) facility.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH); Japan Synchrotron Radiation Research Institute

Grant/Contract Number:: SC0022215; AC02-76SF00515

OSTI ID:: 2575243

Alternate ID(s):: OSTI ID: 2573979

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 44 Vol. 146; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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