Accessible One-Pot Approach to Syndiotactic Non-Conjugated Pendant Electroactive Polymers via Sequential Radical...

Stereoregular non-conjugated pendant electroactive polymers (NCPEPs) show promising hole mobilities (μh) as measured by space charge limited current (SCLC) but have required rigorous anionic polymerization techniques to obtain higher stereoregularity. Syndiotactic NCPEPs in particular are the subject of only one literature report due to synthetic challenges despite the exceptional reported μh. Here, a facile one-pot sequential synthetic strategy involving the accessible radical photopolymerization of methacrylate salt in water, followed by guanidine mediated post-polymerization modification (PPM) with alkyl bromide-functional pendant carbazole has been developed for synthesizing syndiotactic poly(alkyl methacrylates). This route is not only accessible but also reduces polymer loss through the sequential one-pot nature of the polymerization and functionalization. A poly(N-carbazolylhexyl methacrylate) thus synthesized has 87% triad syndiotacticity (rr), an Mn of 370.5 kg mol-1 and shows μh of 1.36 × 10-3 cm2 V-1 s-1. This approach thus demonstrates a significant improvement in the synthesis of syndiotactic polymethacrylate-based NCPEPs.