Hydrogen-Bonding 3D Networks by Polyhedral Organosilanols: Selective Inclusion of Hydrocarbons in Open Frameworks

Tetrahedral organosilanols E[C6H4Si(i-Pr)2OH]4 (E = C, 2a; E = Si, 2b) as well as octahedral organosilanols Si8O12(CH═CHC6H4SiR2OH)8 (R = i-Pr, 5a; R = Ph, 5b) have been derived from tetraphenylmethane and -silane (1a,b) and octavinyloctasilsesquioxane (3) designed for self-assembly of 3D hydrogen-bonding networks possessing large porosity. X-ray analyses following crystallization of 2a,b from THF/benzene and either hexane or heptane revealed adamantane-type networks with hydrogen bonds between the silanols of four separate molecules and selective inclusion of hexane or heptane, respectively. Upon changing the mixed solvent to THF/benzene/cyclohexane, X-ray analysis of 2a showed an inclusion compound of composition 2a·1.5benzene. TOPOS analyses of 2a·1.5benzene demonstrated a non-adamantane-type framework with sra network topology. Crystallization of 5a,b from acetone/benzene followed by X-ray analyses confirmed the production of the inclusion compounds 5a·18benzene and 5b·23benzene. The open frameworks o...