Programmable Directional Assembly of Hydrogen-Bonded Lead Organic Chalcogenolates

Abstract Controlling the directional assembly of metal organic chalcogenolates (MOCs) with atomic precision remains a synthetic challenge yet represents a critical step toward advancing their programmable syntheses and property investigations. Herein, we present a “hydrogen-bond-directed assembly” strategy to drive the formation of single-crystalline, hydrogen-bonded lead organic chalcogenolates (H-LOCs), offering an ideal platform for elucidating their structure–property relationships. By strategically functionalizing thiophenol with regiochemically or electronically distinct substituents, we achieved precise control at the ligand–ligand interface, yielding six distinct H-LOC architectures mediated by interlayer, intralayer, or cooperative hybrid hydrogen-bonding interactions. These programmed hydrogen-bonding interactions play an essential role in crystal growth, enabling the formation of large single crystals of two-dimensional (2D) LOCs. Combined structural and optical characterizations reveal a linear correlation between the ligand electronic effects and optical bandgaps of the materials, culminating in a narrow bandgap of 1.55 eV for the most electron-donating substituent. Most importantly, the reversible nature of these interfacial hydrogen bonds endows the H-LOCs with excellent solution-processability, allowing them to be fabricated into highly stable films with ambient durability exceeding two months─thereby unlocking their potential for optoelectronic devices.