Metal Halide Analogues of Chalcogenides:  A Building Block Approach to the Rational Synthesis of Solid-State Materials

Principles of solid-state structure and bonding that relate metal-halide and metal-chalcogenide materials are described through a comparison of binary AX n salts. Structural variation is rationalized by a comparison of the size and charge of the respective ions, the d-electron count of the cations, and the type of A−X, A−A, and X−X bonding interactions. These general bonding considerations are exploited for the construction of new metal-halide structure types that are patterned after known chalcogenide structures such as metal-halide analogues of silicates, aluminosilicates, phosphates, and phosphonates.