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Liquid crystalline dimers and dimesogens have attracted significant attention due to their tendency to exhibit twist-bend modulated nematic (N TB ) phases. While the features that give rise to N TB  phase formation are now somewhat understood, a comparable structure–property relationship governing the formation of layered (smectic) phases from the N TB  phase is absent. In this present work, we find that by selecting mesogenic units with differing polarities and aspect ratios and selecting an appropriately bent central spacer we obtain a material that exhibits both N TB  and intercalated smectic phases. The higher temperature smectic phase is assigned as SmC A  based on its optical textures and X-ray scattering patterns. A detailed study of the lower temperature smectic ‘’X’’ phase by optical microscopy and SAXS/WAXS demonstrates this phase to be smectic, with an in-plane orthorhombic or monoclinic packing and long (>100 nm) out of plane correlation lengths. This phase, which has been observed in a handful of materials to date, is a soft-crystal phase with an anticlinic layer organisation. We suggest that mismatching the polarities, conjugation and aspect ratios of mesogenic units is a useful method for generating smectic forming dimesogens.

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Experimental and Computational Study of a Liquid Crystalline Dimesogen Exhibiting Nematic, Twist-Bend Nematic, Intercalated Smectic, and Soft Crystalline Mesophases