Click Functionalization of a Dibenzocyclooctyne‐Containing Conjugated Polyimine

Abstract A conjugated poly(phenyl‐ co ‐dibenzocyclooctyne) Schiff‐base polymer, prepared through polycondensation of dibenzocyclooctyne bisamine (DIBO‐(NH 2 ) 2 ) with bis(hexadecyloxy)phenyldialdehyde, is reported. The resulting polymer, which has a high molecular weight ( M n >30 kDa, M w >60 kDa), undergoes efficient strain‐promoted alkyne–azide cycloaddition reactions with a series of azides. This enables quantitative modification of each repeat unit within the polymer backbone and the rapid synthesis of a conjugated polymer library with widely different substituents but a consistent degree of polymerization (DP). Kinetic studies show a second‐order reaction rate constant that is consistent with monomeric dibenzocyclooctynes. Grafting with azide‐terminated polystyrene and polyethylene glycol monomethyl ether chains of varying molecular weight resulted in the efficient syntheses of a series of graft copolymers with a conjugated backbone and maximal graft density.