with long-range order have been prepared by a classical sol-gel process. Precursors such as (MeO)₃Si-R-Si(OMe)₃, R being a thermotropic mesogen-like organic group, have been studied and a self-association process in solution between the molecular units during the formation of the Si-O-Si network is found. (R. J. P. Corriu et al., August 5, Adv. Mater. 2002, 14, 1081-1084)