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

Metal Organic Chalcogenolates (MOChas) are a class of robust, self-assembling, and hybrid materials featuring inorganic metal-chalcogen frameworks that are scaffolded by organic ligands. Ligand selection of MOChas to guide inorganic formation offers a versatile platform for structural and electronic tunability. In this work, we report two new silver benzenethiolate MOChas with hydroxy and amine, which exhibit hydrogen-bond-driven supramolecular organization and novel inorganic connectivities, and contextualize these compounds as distinct outcomes within a structural continuum. Silver para- and meta-methoxy-benzenethiolates serve as control points for known 2D and 1D topologies, respectively. The materials were structurally characterized using small molecule serial femtosecond crystallography, and their energetic and electronic properties were confirmed through density functional theory calculations. We introduce the concept of supra-molecular distortion to describe how ligand-driven intermolecular interactions reshape inorganic topology, establishing a design paradigm which links organic ligand identity to predictable shifts in inorganic dimensionality in MOChas.