Star and miktoarm star block (co)polymers via self-assembly of ATRP generated polymer segments featuring Hamilton wedge and cyanuric acid binding motifs

Hamilton wedge (HW) end-functionalized poly(styrene) (PS-HW, M_n = 5400 g mol^-1, PDI = 1.06), HW mid-chain functionalized poly(styrene) (PS-HW-PS, M_n = 4600 g mol^-1, PDI = 1.04), cyanuric acid (CA) end-functionalized poly(styrene) (PS-CA, M_n = 3700 g mol^-1, PDI = 1.04) and CA end- functionalized poly(methyl methacrylate) (PMMA-CA, M_n = 8500 g mol^-1, PDI = 1.13) precursors were successfully synthesized via a combination of atom transfer radical polymerization (ATRP) and copper catalyzed azide-alkyne cycloaddition (CuAAC). The precursor polymers were characterized via size exclusion chromatography (SEC) and 1H NMR with respect to both molecular weight and structure. Supramolecular homopolymer (PS-HW-PS-CA), block copolymer (PS-HWPMMA-CA), star polymer (PS-HW-PS - PS-CA) as well as miktoarm star polymer (PS-HW-PS - PMMA- CA) were formed in solution in high yields at ambient temperature (association close to 89% for PS-HW-PS-CA, 90% for PS-HW-PS - PS-CA and 98% for PS-HW-PS - PMMA-CA) via H-bonding between the orthogonal recognition units, HW and CA. The formation of supramolecular polymers was confirmed via 1H NMR at ambient temperature in deuterated methylene chloride (CD ₂Cl₂) solution.