Nucleophilic Displacement Reactions of Silver-Based Metal-Organic Chalcogenolates

Area of Science:

• Materials Science
• Inorganic Chemistry
• Crystallography

Background:

• Metal-organic chalcogenolates (MOChas) are crystalline materials with tunable 1D or 2D inorganic topologies.
• Current MOCha synthesis often limited by small ligands, leading to poor morphology and indeterminate structures.
• Larger ligands are desirable for creating more complex MOChas but are challenging to incorporate.

Purpose of the Study:

• To overcome limitations in MOCha synthesis by developing a novel ligand exchange strategy.
• To enable the preparation of higher-dimensional MOChas and incorporate larger organic ligands.
• To investigate the mechanism of ligand exchange in MOChas.

Main Methods:

• Ligand exchange reaction using a 1D MOCha (silver(I) methyl 2-mercaptobenzoate) as a silver source for 2D MOCha synthesis.
• Characterization of reaction products and mechanistic studies of chalcogenol and dichalcogenide exchange.
• Small-molecule serial femtosecond crystallography (smSFX) for structural determination of novel MOChas.

Main Results:

• Demonstrated successful synthesis of 2D MOChas from 1D precursors via nucleophilic displacement.
• Showed preference for displacing 1D topologies to yield 2D ones and thiolates with selenolates.
• Successfully prepared previously inaccessible oligophenyl MOChas using this method.

Conclusions:

• The developed ligand exchange strategy provides a new synthetic route for elaborate MOChas and heterostructures.
• This method facilitates the incorporation of larger, more complex organic ligands into MOCha frameworks.
• The study elucidates the nucleophilic substitution mechanism governing ligand exchange in MOChas.