Hexylene- and octylene-bridged polysilsesquioxane hybrid crystals self-assembled by dimeric building blocks with ring structures.

We report the synthesis of novel polysilsesquioxane hybrid crystals prepared from two precursors with hexylene- and octylene-bridged groups. Both crystals are composed of bimolecular rings (18- and 22-membered, respectively) formed by one-step condensation of two hydrolyzed monomers. The hydrogen bonds between silanol groups and the weak van der Waal's interactions between alkyl chains link the large rings as building blocks together into self-assembled, three-dimensional molecular crystalline structures. The precise control of the sol-gel process is considered to be the crucial factor in fabricating flexible long alkyl chains into an ordered stacking. These contributions extend the understanding of the sol-gel chemistry of polysilsesquioxanes.