Thermodynamic and diffraction analyses were performed to establish the phase diagram for a binary system between 4-n-nonyl-4'-isothiocyanatobiphenyl (9TCB) and n-nonane. The swollen SmE structure is identified in the binary system. Upon swelling, a characteristic two-dimensional herringbone array is maintained whereas the layer spacing of SmE structure increases with the content of n-nonane. Considering the difficulties in explaining the experimental findings based on the traditional model of SmE structure, a new model, lamellar with two types of sublayers consisting of aromatic core and alkyl chain moieties, is proposed.

To confirm the molten state of the alkyl chain in soft crystalline phase, smectic E (SmE) phase, thermodynamic and spectroscopic analyses were performed on 4-n-alkyl-4′-isothiocyanatobiphenyl (nTCB, n: the number of carbon atoms in the alkyl group). DSC results of 11TCB and 12TCB, having extra smectic A phase besides smectic E phase, show that their chain-length dependence of entropies of transition (Δtrs S) from the ordered crystalline (OC) phase to the SmE phase matches the trend found for nTCB (n = 4–10), while no chain-length dependence is observed in Δtrs S at the SmE-to-SmA and SmA-to-isotropic liquid (IL) phase transitions in 11TCB and 12TCB. Temperature dependences of FT-IR spectra of six compounds (n = 2, 3, 5, 8, 10, and 12) were recorded. The CH stretching modes of the chain exhibited more pronounced change at the transition from the OC to the SmE phase than at the transition from the SmE phase to the IL or SmA phase. These results indicate that the alkyl chain is molten in the SmE phase as in IL. The disordering process of nTCB molecules from the OC to IL via anisotropic mesophases is discussed in terms of entropy.

Based on new diffraction data from aligned samples of smectic E (SmE) phase of 4-n-alkyl-4'-isothiocyanato-1,1'-biphenyls, systematics against the alkyl chain length n is analyzed. In order to perform the analysis, the molecular form factor approximated by a box-shaped distribution is calculated while taking the rounding of the distribution at corners into account. The analysis clearly shows the nano-segregated layered structure, which does not fit to the traditional structural view of SmE phase but does fit to the model the present authors proposed recently. Some implications of this conclusion are discussed in relation to the importance of the molten state of alkyl chains in most of real mesogens revealed previously through thermodynamic analyses.

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