Tubular Architectures from Polymers with Tapered Side Groups. Assembly of Side Groupsviaa Rigid Helical Chain Conformation and Flexible Helical Chain Conformation InducedviaAssembly of Side Groups

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 (Φ h ) 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 Φ h 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.