Pairs of bifunctional initiators have been designed that carry complementary hydrogen-bonding sites consisting of alternatingly placed multiple acceptors (A) and donors (D) (e.g., �ADA�) between two initiating halogens for metal-catalyzed living radical polymerization. These initiators give well-defined polymers with an A/D hydrogen-bonding sites at the center of a polymer backbone, to form X-shaped supramolecular self-assemblies [Macromolecules 2012  , 45(9), 3702-3710]. Such positionally induced association is interesting in that it would lead to advanced self-assemblies without changing polymer backbone structures.Following the lead, this work was directed to introducing the multiple complementary A/D interactive sites in a regular interval along a polymer chain. Radical oligomerization was first initiated with the designed bifunctional initiator (e.g., Cl�DAD�Cl or Cl�DADDAD�Cl) to obtain oligomers of controlled molecular weights. Subsequent chain extension by radical coupling led to the target polymers with regularly positioned multiple recognition sites, �(~~DAD~~)n� or �(~~DADDAD~~)n�, respectively. Supramolecular self-assemblies are also examined for these self-complimentary polymer pairs, such as �(~~DAD~~)n� and �(~~ADA~~)m�.

Periodic introduction of complementary interactive sites onto polymer chains toward novel self-assemblies

246th National Meeting (2013)

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