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) were designed for self-assembly of 3D hydrogen-bonding networks possessing large porosity. Depending on the pore size, hydrocarbons such as hexane and heptane were included in the open frameworks without interpenetration of the networks. Furthermore, as a guest ...