Stabilization of the bicontinuous cubic phase in siloxane-terminated mesogens, 1,2-bis[4′-(n-(oligodimethylsiloxyl)alkoxy)benzoyl]hydrazine†
The introduction of oligodimethyl siloxane segments at the termini of the alkyl tails has been employed to stabilize the bicontinuous cubic (Cubbi) phase of a chain-core-chain type molecule having a 1,2-bis(benzoyl)hydrazine central core with two chains attached at the 4′ position of each benzoyl moiety. In this study, three silylated molecules, bis-C10Si2, bis-C10Si3, and C10Si2-C8CC, were synthesized, where “CnSim” represents the number of carbon and silicon atoms in the chain and “bis” indicates the two chains being the same, whereas the last one is asymmetric with respect to the core. The phase behaviors were examined by using polarized optical microscopy, differential scanning calorimetry, and X-ray diffraction techniques. All three compounds form Cubbi phases and their syntheses were compared including their parent compound bis-C18. It was clearly revealed that the introduction of oligodimethyl siloxane segments effectively suppresses the crystallization at low temperatures, and as a result stabilizes the Cubbi phases, in an extreme case down to room temperature. The semi-quantitative analyses in terms of lattice constant and three-dimensional electron density map help us to better understand the self-assembly process in the Cubbi phases. The study also revealed that the introduction of oligodimethyl siloxane segments is not only an alternative for the hydrocarbon segment but also is able to provide a versatile design strategy for obtaining stable Cubbi phases.