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X-Shaped ternary five-block molecules, composed of a rigid p-terphenyl core, two terminal glycerol groups and two flexible n-alkyl or semiperfluorinated chains fixed laterally to opposite sides of the terphenyl moiety, form liquid crystalline phases built up of honeycomb-like arrays of polygonal cylinders, where the rod-like aromatic cores form cylinder walls with a thickness equal to the width of a single molecule.

Graphical abstract: X-Shaped polyphilics: liquid crystal honeycombs with single-molecule walls

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