A stoichiometrically conserved homologous series with infinite structural diversity

We describe a compositionally guided structural evolution within a stoichiometrically conserved framework, BaSbQ₃ (Q = Te_1-<i>_x</i>S<i>_x</i>), where each value of <i>x</i> gives rise to a distinct phase. The fundamental building blocks, <i>A</i>₁ (BaSbSTe₂) and <i>B_n</i> (Ba<i>_n</i>Sb<i>_n</i>S<i>_n</i>_-1Te₂<i>_n</i>₊₁), were composed of modular double rocksalt slabs stacked with functional polytelluride zigzag chains, with each phase differing only in the size and assembly of these blocks. Ten compounds were synthesized that maintained a coherent chemical identity that arose from this isovalent, isoelectronic substitution of Te and S. We envision that the phase formation at a molecular level unfolds in stages of extension, termination, and assembly and propose a design concept of "anionic disparity," where phase homologies and polytelluride hierarchical networks can be controlled by leveraging differences in anion electron affinity and sizes.