Guest subset guest subset host multicomponent molecular crystals: entrapment of guest subset 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 subset guest subset 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.