Precise synthesis of double-armed polymers with fullerene C60 at the junction for controlled architecture

Abstract

Fullerene-containing polymers offer the unique opportunity to fabricate self-assembled nanostructures and organic electronics. The synthesis of well-defined fullerene-containing polymers, having double polymeric chains attached to fullerene in a regioselective manner, is a fundamental challenge in both synthetic organic chemistry and precision polymer chemistry. Here, inspired by the state-of-the-art fullerene chemistry, we present a new strategy for the stepwise synthesis of double-armed polymers with fullerene C₆₀ at the junction in high reaction yields and with high selectivity. First, poly(styrene)-attached 1,2-hydrofullerene (1,2-PS-C₆₀-H) was synthesized via the cobalt-catalyzed radical addition reaction. Next, the fullerenyl anion, 1,2-PS-C₆₀⁻, was reacted with bromo-terminated poly(acetoxystyrene) to generate diblock copolymer 1,4-bisadducts (1,4-PS-C₆₀-PAS). This example highlights the applicability of polymeric 1,4-fullerene bisadducts for self-assembling building blocks and potential organic electronics.