Pillararene-Based Variable Stoichiometry Co-Crystallization: A Versatile Approach to Diversified Solid-State Superstructures

Variable stoichiometry co-crystals are important in solid-state supramolecular chemistry as they allow studies of structure–property relationships while permitting the synthesis of new scaffolds using identical synthons. In this work, we extend the concept of variable stoichiometry co-crystals into the realm of pillararene chemistry and show that this permits the rational construction of a diverse set of supramolecular structures in the solid state. Specifically, we report a series of variable stoichiometry co-crystals based on pillar­[n]­arenes and tetracyanobenzene (TCNB) and show that the combination of in-cavity complexation by pillar­[n]­arenes (n = 5,6) and outside binding with TCNB allows several types of co-crystals with different self-assembled superstructures to be isolated. The variable stoichiometry co-crystals of this study display different solid-state physicochemical properties, including colors and luminescence features. Among these pillar­[n]­arene-based co-crystals, we discovered unique crystallographic architectures wherein two sets of individual host–guest complexes co-exist in the solid state. These mixed co-crystal systems allow for vapochromic-based detection of n-bromoalkanes. This work highlights a new strategy for the construction of self-assembled superstructures in the solid state and for tuning their intrinsic characteristics, including their luminescent and substrate-responsive features.