Combining Modular Ligation and Supramolecular Self‐Assembly for the Construction of Star‐Shaped Macromolecules

A well‐defined random copolymer of styrene (S) and chloromethylstyrene (CMS) featuring lateral chlorine moieties with an alkyne terminal group is prepared (P(S‐ co ‐CMS), $\overline{M}_{\rm n}$ = 5500 Da, PDI = 1.13). The chloromethyl groups are converted into Hamilton wedge (HW) entities (P(S‐ co ‐HWS), $\overline{M}_{\rm n}$ = 6200 Da, PDI = 1.13). The P(S‐ co ‐HWS) polymer is subsequently ligated with tetrakis(4‐azidophenyl)methane to give HW‐functional star‐shaped macromolecules (P(S‐ co ‐HWS)) 4 , $\overline{M}_{\rm n}$ = 25 100 Da, PDI = 1.08). Supramolecular star‐shaped copolymers are then prepared via self‐assembly between the HW‐functionalized four‐arm star‐shaped macromolecules ( P(S‐ co ‐HW )) 4 and cyanuric acid (CA) end‐functionalized PS (PS–CA, $\overline{M}_{\rm n}$ = 3700 Da, PDI = 1.04), CA end‐functionalized poly(methyl methacrylate) (PMMA–CA, $\overline{M}_{\rm n}$ = 8500 Da, PDI = 1.13) and CA end‐functionalized polyethylene glycol (PEG–CA, $\overline{M}_{\rm n}$ = 1700 Da, PDI = 1.05). The self‐assembly is monitored by 1 H NMR spectroscopy and light scattering analyses.