We have performed time resolved diffraction experiments in order to obtain a better insight upon the metastable phases surrounding some thermotropic mesophases of cubic Ia 3 d and Im 3 m symmetries. These metastable phases are columnar hexagonal, smectic or tetragonal, depending on the nature of the mesogenic molecule. Moreover, it appears that the structure of the cubic phase of the 4-alkyloxybiphenyl-4-carboxylic acids previously labelled smectic D varies with the lateral group substituted on the biphenyl core.