Syntheses of N-[3,4,5-tris(n-dodecan-1-yloxy)phenyl]maleimide (6) and exo,exo-5,6-bis[[[3,4,5-tris(n-dodecan-1-yloxy)benzoyl]oxy]methyl]-7-oxabicyclo[2.2.1]hept-2-ene (16) and their polymerization by radical, anionic and ring opening metathesis polymerizations, respectively, to yield the corresponding polymers 7 and 17 are described. Regardless of the polymerization method by which it was synthesized, 7 produced a hexagonal columnar (Φh) liquid crystalline phase generated from the tubular architecture of the rigid 7/2 helical chain conformation surrounded by its tapered side groups. 17 also produces a Φh phase. However, in this case, the assembly of tapered side groups of 17 into a tubular architecture induced a 3/1 helical chain conformation of its own flexible backbone. These two experiments support the model in which polymers containing tapered side groups form tubular supramolecular architectures by inducing a flexible helical chain conformation during the self-assembly of their own tapered side groups or by favoring the self-assembly of tapered side groups when a suitable rigid helical chain conformation is adopted by their own backbone.

The synthesis of the first generation AB 3 monodendrons 3,4,5-tris[6-alkyloxy-2-methylnaphthyloxy]benzoic acid (with decyl, dodecyl, tetradecyl, and hexadecyl alkyl groups), 3,4,5-tris[4-(4′dodecyloxyphenyl)benzyloxy]benzoic acid, their ω-hydroxy(tetraethylene glycol) esters, and the corresponding methacrylates and poly(methacrylate)s is described. All monodendrons and the corresponding polymers self-assemble into supramolecular columns that self-organize in a columnar hexagonal (Φh) thermotropic liquid crystalline (LC) phase. The characterization of their Φh phase by a combination of differential scanning calorimetry (DSC), thermal optical polarized microscopy, and X-ray diffraction experiments demonstrated an intracolumnar microsegregated model for these supramolecular structures. The role and the contribution of the aliphatic, aromatic, oligooxyethylenic, and polymethacrylate fragments to the formation and the control of the external diameter, the internal structure, and the stability of these supramolecular columns and of the Φ h phase were quantitatively evaluated and demonstrated that the contribution of the aromatic component dominates over that of the other structural components both in the control of column diameter and in thermodynamic stability of the resulted Φh phase. Scheme 2. Synthesis of 3,4,5-tris-[n-alkyloxy]benzoic Acid Derivatives, 8-n-Nf (n ) 10, 12, 14, 16) and 8-12-Bp

The tapered building blocks 3,4,5-tris[(4-(n.-decan-l-yloxy)benzyl)oxy]benzoic acid (8-10/0), 3,4,5-tris[(4-((