Isomorphism within the hexagonal columnar mesophase of molecular and macromolecular self- and co-assembled columns containing tapered groups

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Abstract
The phase behaviour of binary mixtures of self-assembled tapering molecules based on monoesters of oligooxyethylene glycol and 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoic acid, their corresponding polymethacrylates, and of 4′-methyl (benzo-15-crown-5)-3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate within their hexagonal columnar mesophase (Φh) is described. The binary blends between molecular tapers co-assemble into a single supramolecular column resulting in isomorphism within their Φh mesophase over the entire range of composition. The binary blends between polymethacrylates containing tapered side groups co-assemble into a single Φh phase only when the columns of the parent polymers are of similar diameters. This results in binary mixtures which are isomorphic within the Φh mesophase over the entire composition range. When the diameters of the columns formed by the parent polymers are dissimilar, isomorphic mixtures are obtained only over a narrow range of composition. Binary mixtures between molecular tapers and macromolecular systems containing tapered side groups co-assemble into a single column to the extent that intercalation of the molecular taper, within the column formed by the macromolecular system containing tapered side groups, is permissible. In all systems increased intracolumnar interactions can be induced by complexation of CF3SO3Li by the oligooxyethylenic receptors leading to isomorphism in otherwise non-isomorphic mixtures. Ternary mixtures between molecular tapers with non-specific oligooxyethylenic receptors and specific crown ether receptors and CF3SO3 Na as the third component are non-isomorphic within their Φh phase due to preferential complexation of the alkali metal cation by the column of the crown ether containing the molecular taper. This results in two columns of dissimilar diameters, which are isomorphic in the Φh phase only within a limited range of composition.