Synthesis of Supramolecular A 8 B n Miktoarm Star Copolymers by Host-Guest Complexation.

We report a new synthetic method to construct supramolecular A 8 B n (n=1, 2, 4) miktoarm star copolymers by host-guest complexation between a resorcinarene-based coordination capsule possessing eight polystyrene chains and 4,4-diacetoxybiphenyl guest molecules that retain one, two or four polymethyl acrylate chains. The formation of the supramolecular A 8 B n (n=1, 2, 4) miktoarm star copolymers was confirmed by dynamic light scattering (DLS), size-exclusion chromatography (SEC), and diffusion-ordered NMR spectroscopy (DOSY). Differential scanning calorimetry (DSC) measurements revealed that the miktoarm copolymers were phase-separated in the bulk. The micro-Brownian motion of the A 8 B 4 structure was markedly enhanced in the bulk due to a weak segregation interaction between the immiscible arms.