Discovery-Synthesis, Design, and Prediction of Chalcogenide Phases.

The discovery of new materials and their efficient syntheses is a fundamental goal of chemistry. A related objective is to identify foundational and rational approaches to enhance the art of synthesis by combining the exquisite predictability of organic synthesis with the high yields of solid-state chemistry. In contrast to so-called solid-state methods, inorganic syntheses in liquid fluxes permit bond formation, framework assembly, and crystallization at lower temperatures because of facile diffusion and chemical reactions with and within the flux itself. The fluxes are bona fide solvents similar to conventional organic or aqueous solvents. Such reactions can produce a wide range of materials, often metastable, from oxides to intermetallics, but typically the formation mechanisms are poorly understood. This article discusses how one can design, perform, observe, understand, and engineer the formation of compounds from inorganic melts. The focus is also design concepts such as "dimensional reduction", "phase homologies", and "panoramic synthesis", and their broad applicability. When well-defined building blocks are present and stable in the reaction, prospects for increased structural diversity and product control increase substantially. Common structural motifs within these materials systems may be related to structural precursors in the melt that may be controlled by tuning reaction conditions and composition. Stabilization of a particular building block is often accomplished with tuning of the flux composition, which controls the Lewis basicity and redox potential. In such tunable and dynamic fluxes, the synthesis can be directed toward new materials. Using complementary techniques of in situ X-ray diffraction, we can create time-dependent maps of reaction space and probe the mobile species present in melts. Certain thoughts toward the ultimate goal of targeted materials synthesis by controlling inorganic melt chemistry are discussed.