Tubular Architectures from Polymers with Tapered Side Groups. Assembly of Side Groups<i>via</i>a Rigid Helical Chain Conformation and Flexible Helical Chain Conformation Induced<i>via</i>Assembly of Side Groups

Abstract

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.