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 meta-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 para- and meta-methoxy-benzenethiolates (p-OCH₃ and m-OCH₃) serve as control points for known 2D and 1D topologies, respectively. The new materials, m-OH and m-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 supramolecular distortion 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.