Guest⊂Guest⊂Host Multicomponent Molecular Crystals: Entrapment of Guest⊂Guest in Honeycomb Networks Formed by Self‐Assembly of 1,3,5‐Tri(4‐hydroxyaryl)benzenes

Sterically‐engineered rigid trigonal molecular modules based on 1,3,5‐tri(4‐hydroxyphenyl)benzenes H1 and H2 undergo O‐H⋅⋅⋅O hydrogen‐bonded self‐assembly into eight‐fold catenated hexagonal (6,3) and two‐fold interpenetrated undulated square (4,4) networks, respectively. In the presence of [18]crown‐6 as a guest, the triphenol H1 is found to self‐assemble into a honeycomb network with hexagonal voids created between three triphenol building blocks. The guest [18]crown‐6 molecules are found to be nicely nested in hexagonal enclosures. The empty spaces within the crowns can be further filled with neutral (MeOH/water, MeOH/MeNO 2 ) or ionic guest species such as KI/KAcAc to furnish novel multicomponent assemblies, that is, guest ⊂ guest ⊂ host, that typify Russian dolls. In contrast, triphenol H2 is found to yield analogous multicomponent molecular crystals in which the guest crown–K + acts as a spacers in the hydrogen‐bonded self‐assembly that leads to distorted chicken wire networks.