Chelation-Driven Dissolution and Single-Crystal Growth of Hybrid Metal Organochalcogenide Semiconductors by Polydentate Amines

The ability to grow single crystals is critical to modern society, particularly forming the foundation of the semiconductor industry that drives transformative innovations. While inorganic semiconductors are typically grown using melt-based methods, and organic semiconductors via solution processing, these approaches are often unsuitable for hybrid organic-inorganic semiconductors, which tend to exhibit low thermal stability and high solvent resistance. Here, we report a general solution-based strategy to overcome this challenge by exploiting polydentate amine solvents to dissolve and recrystallize previously intractable metal organochalcogenides (MOCs)─an emerging family of hybrid semiconductors, with potentials for robust luminescence, strong exciton binding energy, and electronic anisotropy. Using silver phenylselenide as a model system, we show that chelation-driven solubility in amines enables the growth of up to 1.02 cm × 0.54 cm single crystals with enhanced spectral purity, and that this strategy is general across MOC derivatives with diverse organic and chalcogen components. Recrystallization from these solvents yields high-quality single crystals of 15 MOCs, including eight previously unreported structures and three adopting noncentrosymmetric or polar space groups. Mechanistic studies reveal that dissolution proceeds via fragmentation into neutral, nanoscale polymeric units rather than ionic dissociation. These findings not only deepen the understanding of MOC solubility but also establish a broadly applicable platform for accessing single crystals of hybrid semiconductors. Together with the observation that several MOCs adopt 2D layered and noncentrosymmetric architectures, this work positions MOCs as a new family of next-generation, solution-processable semiconductors and opens avenues for crystallizing other insoluble hybrid materials.