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-(NH2)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.