| Abstract Scope |
The discovery of new inorganic solids is often viewed as a search across vast composition and structure spaces. Yet new materials emerge through reaction pathways governed by bonding preferences, oxidation states, solubility, reaction media, temperature, competing phases, and kinetics. Chemical intuition remains essential for identifying the variables and constraints that enable more effective data-driven materials discovery. This perspective is illustrated with two examples. First, mixed hydroxide-halide fluxes serve as tunable high-temperature solvents that control reactant solubility and redirect chalcogenide synthesis, leading to the discovery of more than 30 new compounds spanning over ten structure types while revealing systematic links between reaction conditions and structural outcomes. Second, the BaSbQ3 (Q = Te/S) system demonstrates how a stoichiometrically conserved homologous series can generate remarkable structural diversity through modular building blocks, providing a structural grammar that enables prediction of new compounds. These examples will aim to show how chemical intuition can guide and constrain data-driven approaches, making materials discovery more efficient, reliable, and successful. |