Guest-adaptive hydrogen-bonded dimerization of a C3-symmetric tribenzotriquinacene molecular bowl

Abstract

Hydrogen-bonded dimerization of a C₃-symmetric tribenzotriquinacene-based molecular bowl (C₃-1) orchestrates the formation of supramolecular assemblies characterized with exceptional guest-induced structural modulation. In the absence of guest molecules, C₃-1 assembles into π⋯π stacking dimers devoid of a predefined cavity, yet it exhibits remarkable structural plasticity upon guest binding. The introduction of small aromatic and aliphatic guests—including cyclohexane, benzene, and o-/m-/p-xylene—triggers dynamic, self-adaptive structural transformations, culminating in the formation of host–guest complexes with distinct architectures. X-ray crystallography reveals pronounced structural variations among these assemblies, underscoring the pivotal role of hydrogen bonding and host–guest interactions in directing supramolecular organization. This study illuminates a versatile design paradigm for tribenzotriquinacene-based molecular cages with tunable properties, offering promising candidates for applications in molecular recognition, selective encapsulation, and crystal sponge technologies.