Six-Component Molecular Solids: ABC[D1–(x+y)ExFy]2

A strategy has been developed to achieve six-component molecular solids. The first part of the protocol involves the design and development of a family of stoichiometric quaternary cocrystals. It relies on the idea that when a molecule is in two distinct crystallographic environments in a lower-order cocrystal it becomes susceptible to substitution by a new molecule at the site where it is more weakly bound, if it is enthalpically advantageous to do so. Accordingly, a binary cocrystal acts as a stepping stone to a ternary, and so on. However, the subject system ran into a synthetic dead end at the level of quaternary cocrystals, in that no further crystallographic inequivalences could be found. This necessitated the development of the second part of the protocol, which exploits the shape-size similarities of 2-chloro-, 2-bromo-, and 2-methylresorcinols (CRES, BRES, and MRES respectively) and circumvents this synthetic dead end to achieve several five-and six-component solids, wherein the fifth and sixth components are incorporated in a solid solution fashion at the site of the fourth component.