Synthesis of Supramolecular A8Bn 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.

Automated summary

We developed a new synthetic method to construct supramolecular A(8)B(n) (n=1, 2, 4) miktoarm star copolymers through host-guest complexation. The formation of these copolymers was confirmed by various analytical techniques. The miktoarm copolymers exhibited phase separation in bulk, and the micro-Brownian motion of the A(8)B(4) structure was enhanced due to weak segregation interaction between immiscible arms.