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In sharp contrast to molecular synthesis, materials synthesis is generallypresumed to lack selectivity. The few known methods of designing selectivity insolid-state reactions have limited scope, such as topotactic reactions orstrain stabilization. This contribution describes a general approach forsearching large chemical spaces to identify selective reactions. This novelapproach explains the ability of a nominally "innocent" Na$_2$CO$_3$ precursorto enable the metathesis synthesis of single-phase Y$_2$Mn$_2$O$_7$ -- anoutcome that was previously only accomplished at extreme pressures and whichcannot be achieved with closely related precursors of Li$_2$CO$_3$ andK$_2$CO$_3$. By calculating the required change in chemical potential acrossall possible reactant-product interfaces in an expanded chemical spaceincluding Y, Mn, O, alkali metals, and halogens, using thermodynamic parametersobtained from density functional theory calculations, we identify reactionsthat minimize the thermodynamic competition from intermediates. In this manner,only the Na-based intermediates minimize the distance in the hyperdimensionalchemical potential space to Y$_2$Mn$_2$O$_7$, thus providing selective accessto a phase which was previously thought to be metastable. Experimental evidencevalidating this mechanism for pathway-dependent selectivity is provided byintermediates identified from in situ synchrotron-based crystallographicanalysis. This approach of calculating chemical potential distances inhyperdimensional compositional spaces provides a general method for designingselective solid-state syntheses that will be useful for gaining access tometastable phases and for identifying reaction pathways that can reduce thesynthesis temperature, and cost, of technological materials.

Selectivity in yttrium manganese oxide synthesis via local chemical potentials in hyperdimensional phase space