Stabilizing Structural Transitional States between 1- and 2-Dimensional Topologies via Hydrogen Bond-Mediated Crystal Engineering

Metal-organic chalcogenolates (MOChas) are hybrid materials composed of metal-chalcogenide networks coordinated by organic ligands, offering a versatile platform for structural and electronic tunability. The use of molecular ligand design to steer material formation represents a powerful strategy for accessing new solid-state topologies. In this work, we report two new silver benzenethiolate MOChas incorporating protic <i>meta</i>-functionalized ligands─hydroxy (-OH) and amine (-NH<sub>2</sub>)─which exhibit hydrogen-bond-driven supramolecular organization and novel inorganic connectivities. Rather than modifying existing materials, we contextualize these compounds as distinct outcomes within a structural continuum. Silver <i>para-</i> and <i>meta</i>-methoxy-benzenethiolates (<i>p</i>-OCH<sub>3</sub> and <i>m</i>-OCH<sub>3</sub>) serve as control points for known 2D and 1D topologies, respectively. The new materials, <i>m-</i>OH and <i>m</i>-NH<sub>2</sub>, were structurally characterized using small molecule serial femtosecond crystallography (smSFX), and their intermediate energetic and electronic properties were confirmed through density functional theory (DFT) calculations. We introduce the concept of <i>supramolecular distortion</i> to describe how ligand-driven intermolecular interactions reshape inorganic topology─not as deviations from a fixed state, but as distinct, kinetically accessible ground-state architectures. This work establishes a design paradigm linking organic ligand identity to predictable shifts in inorganic dimensionality in MOChas.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2026-03-26
DOI
https://doi.org/10.1021/jacs.5c09213
Primary Topic
Crystallography and molecular interactions
Type
article
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article

Stabilizing Structural Transitional States between 1- and 2-Dimensional Topologies via Hydrogen Bond-Mediated Crystal Engineering

Aaron S. Brewster, C. Milne, Patience A. Kotei, Hazem Yousef et al.
Journal of the American Chemical Society
Crystallography and molecular interactions
article

Stabilizing Structural Transitional States between 1- and 2-Dimensional Topologies via Hydrogen Bond-Mediated Crystal Engineering

Aaron S. Brewster, C. Milne, Patience A. Kotei, Hazem Yousef, Mohammad Vakili, Joana Valério, Ichiro Inoue, J. Nathan Hohman, Dmitry Khakhulin, Matthias Zeller, Daniel Paley, Doriana Vinci, Elyse Schriber, Kensuke Tono, Adriana Ladera, Vanessa Oklejas, Shigeki Owada, Tess Smidt, Adam Round, David Moreau, Nicholas K. Sauter, Yohei Uemura, Marco Kloos, Mariya Aleksich, A. Mancuso, Maggie C. Willson, Komal Rani, F. Alves Lima, Kara Christensen, Aria Mansouri Tehrani, Fernando Ardana-Lamas, Avery LaMonica
article en

Abstract

Metal-organic chalcogenolates (MOChas) are hybrid materials composed of metal-chalcogenide networks coordinated by organic ligands, offering a versatile platform for structural and electronic tunability. The use of molecular ligand design to steer material formation represents a powerful strategy for accessing new solid-state topologies. In this work, we report two new silver benzenethiolate MOChas incorporating protic <i>meta</i>-functionalized ligands─hydroxy (-OH) and amine (-NH<sub>2</sub>)─which exhibit hydrogen-bond-driven supramolecular organization and novel inorganic connectivities. Rather than modifying existing materials, we contextualize these compounds as distinct outcomes within a structural continuum. Silver <i>para-</i> and <i>meta</i>-methoxy-benzenethiolates (<i>p</i>-OCH<sub>3</sub> and <i>m</i>-OCH<sub>3</sub>) serve as control points for known 2D and 1D topologies, respectively. The new materials, <i>m-</i>OH and <i>m</i>-NH<sub>2</sub>, were structurally characterized using small molecule serial femtosecond crystallography (smSFX), and their intermediate energetic and electronic properties were confirmed through density functional theory (DFT) calculations. We introduce the concept of <i>supramolecular distortion</i> to describe how ligand-driven intermolecular interactions reshape inorganic topology─not as deviations from a fixed state, but as distinct, kinetically accessible ground-state architectures. This work establishes a design paradigm linking organic ligand identity to predictable shifts in inorganic dimensionality in MOChas.

Journal of the American Chemical Society
University of Connecticut (US), Lawrence Berkeley National Laboratory (US), La Trobe University (AU), Purdue University West Lafayette (US), SLAC National Accelerator Laboratory (US), Diamond Light Source (GB), SPring-8 (JP), Japan Synchrotron Radiation Research Institute (JP), Université Bourgogne Franche-Comté (FR), Linac Coherent Light Source (US), Massachusetts Institute of Technology (US), European X-Ray Free-Electron Laser (DE)
Openalex Percentile: Top 6%
Crystallography and molecular interactions
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