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

Area of Science:

• Materials Science
• Crystallography
• Supramolecular Chemistry

Background:

• Metal-organic chalcogenolates (MOChas) are hybrid materials with tunable structures and electronic properties.
• Ligand design is a key strategy for creating novel solid-state topologies in MOChas.

Purpose of the Study:

• To synthesize and characterize new silver benzenethiolate MOChas with protic functional groups.
• To investigate the role of ligand functionalization in driving supramolecular organization and inorganic connectivity.
• To establish a design paradigm for predicting MOChas structures based on ligand identity.

Main Methods:

• Synthesis of novel silver benzenethiolate MOChas incorporating hydroxy (-OH) and amine (-NH2) ligands.
• Structural characterization using small molecule serial femtosecond crystallography (smSFX).
• Computational analysis using density functional theory (DFT) to determine energetic and electronic properties.

Main Results:

• Two new silver MOChas, m-OH and m-NH2, were synthesized and structurally characterized.
• Hydrogen-bond-driven supramolecular organization and novel inorganic connectivities were observed.
• DFT calculations confirmed intermediate energetic and electronic properties for the new materials.
• The concept of 'supramolecular distortion' was introduced to explain ligand-influenced topological changes.

Conclusions:

• Ligand identity can predictably influence the inorganic dimensionality of MOChas.
• Supramolecular interactions play a crucial role in shaping the ground-state architectures of MOChas.
• This work provides a design paradigm for creating MOChas with tailored structures and properties.