Abstract
<jats:p>Rhodium chalcogenides have rich crystal chemistry and offer opportunities in catalytic chemical transformations, quantum phenomena and devices, and biological applications. However, their solution phase chemistry, particularly the synthesis of specific phases with well-defined dimensionality, remains nascent. Here, we report a colloidal strategy to access multiple air-stable 5-30 nm nanocrystals of binary rhodium chalcogenides, including Rh0.78Se (P63/mmc), 2D (Pm1) RhTe2, 3D (Pa) RhTe2, and Rh3Te8 (R). We demonstrate how the choices of precursors and injection (Tinj) and growth temperatures (Tgrowth) enable their phase selective synthesis. Analyses by powder X-ray diffraction and electron microscopy verify the compositions and phase purities of the different nanocrystalline samples. Density functional theory calculations confirm metallic character of the binary rhodium chalcogenides and unveil the relative stabilities of different RhCh2 polymorphs (Ch = Se, Te). For example, we find that the synthesized trigonal 2D (Pm1) and cubic pyrite-type 3D (Pa) phases of RhTe2 are metastable compared to an as yet unobserved orthorhombic (Pnma) phase. This study unlocks the phase- and dimensionality-selective synthesis of rhodium chalcogenide nanocrystals and provides a foundation for exploring their structure-dependent properties.</jats:p>