Self-Sorting in Polymers

Random and block copolymers containing two different classes of hydrogen-bonding side-chains have been prepared by ring-opening metathesis polymerization. The resulting copolymers can be viewed as “universal polymer backbones” based solely on two competitive hydrogen-bonding pairs. The hydrogen-bonding side chains containing thymine and cyanuric acid-based recognition motifs are shown to self-assemble with their complementary diamido pyridine and isophthalic wedge moieties, respectively, even in the presence of competitive recognition sites, i.e., selective functionalization of the copolymers can be accomplished via a one-step orthogonal self-assembly approach displaying self-sorting in a competitive environment. These results clearly demonstrate the concept of self-sorting in synthetic polymers and suggest the design of complex polymeric materials containing competitive noncovalent interactions.