Orthogonal Modification of Polymers via Thio-Bromo "Click" Reaction and Supramolecular Chemistry: An Easy Method Toward Head-to-Tail Self-Assembled Supramolecular Polymers.

Heterotelechelic poly(n-butyl acrylate)s (PnBuA) bearing two different and complementing supramolecular groups (namely, barbiturate (Ba) and the Hamilton wedge (HW)) at their α-end and ω-end (Ba-PnBuA-HW) were prepared by a combination of the reversible addition-fragmentation chain transfer (RAFT) process and the thio-bromo click reaction. The successful synthesis of the heterotelechelic H-bonding polymer Ba-PnBuA-HW (Mn,NMR = 7700 g/mol, Mn,SEC = 7500 g/mol, PDI = 1.25) was proven by a combination of 1H NMR and MALDI-TOF mass spectrometry. Self-assembly of the resulting heterotelechelic H-bonding polymers (Ba-PnBuA-HW) in a head-to-tail fashion driven by multiple H-bondings in solution and in the bulk was proven by temperature-dependent 1H NMR, concentration-dependent DOSY NMR studies, and rheological measurements.