Aqueous solutions of ternary ortho-chalcogenidostannate anions [SnE(1)(4-x)E(2)(x)](4-) (E(1), E(2) = S, Se, Te) have been generated following different routes that all lead to equilibria of all possible permutations of binary and ternary anions. This has been rationalized by means of NMR studies that can be explained by calculations using density functional theory (DFT) methods. Thus, if one reacts such solutions with transition-metal ions, quaternary M/Sn/E(1)/E(2) anions are obtained, which exhibit coordination by different ternary chalcogenidostannate ligands. The electronic excitation energies of the corresponding alkali metal salts lie between the E(g) values of compounds containing either M/Sn/E(1) or M/Sn/E(2) anions. In this way, we provide a simple approach toward a library of semiconductor compounds with finely-tuned optoelectronic properties.