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Small changes in molecular structure and crystallisation conditions can have a profound effect on the crystal packing of molecules. Increasing the system complexity—for example, by introducing multiple components—greatly increases the number of potential outcomes. Hence, the rational design of porous co-crystals with multiple components is challenging. Here, we report a family of isoreticular quasiracemate crystalline phases for porous organic cages, FT-RCC3-R·CCX-S (where X = 1, 2, or 4), that were prepared in a modular and predictable fashion. By using directional intermolecular interactions between cages, we were able to prepare a rare ternary co-crystal, (CC3-S0.5CC4-S0.5)·(CC13-S0.5CC3-S0.25CC4-S0.25).

Modular assembly of porous organic cage crystals: isoreticular quasiracemates and ternary co-crystal