Synthesis of higher-order cocrystals

Targeted synthesis of higher-order cocrystals containing up to six components has been achieved. The synthesis of stoichiometric quaternary cocrystals has been achieved using the idea of Long-range Synthon Aufbau Modules (LSAMs) and in parallel by utilising 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. Thus, when all the possibilities of strong hydrogen bonds in a system have been satisfied, the crystallization of the system is guided primarily by close-packing, lending it to the possibility of forming solid solutions with molecules which are very close in shape and size and which do not disturb any essential hydrogen bonds in the system.

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