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 (-NH₂)─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>-OCH₃ and <i>m</i>-OCH₃) serve as control points for known 2D and 1D topologies, respectively. The new materials, <i>m-</i>OH and <i>m</i>-NH₂, 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.