Synthesis and Properties of Tetrathiafulvalene End-Functionalized Polymers Prepared via RAFT Polymerization

Abstract

The reversible addition−fragmentation chain transfer (RAFT) polymerization technique has been employed to synthesize various linear tetrathiafulvalene end-functionalized polymers. n -Butyl acrylate, N -isopropylacrylamide, and styrene monomers were polymerized in the presence of azobis(isobutyronitrile) and a new tetrathiafulvalene (TTF) trithiocarbonate derivative as reversible chain transfer agent. All RAFT polymerizations exhibited pseudo-first-order kinetics, a linear increase of the number-average molar mass ( M n SEC) with conversion and narrow molar mass distributions (polydispersity <1.3). The resulting homopolymers exhibited α-TTF and ω-trithiocarbonyl end groups. Cyclic voltammetry was used to investigate the electrochemical properties of the TTF polymers. Finally, we have shown that the TTF moiety at the α-chain-end could be specifically modified by complex formation with the tetracationic cyclophane cyclobis(paraquat- p -phenylene) (CBPQT 4+ ) in organic media. Electrochemical oxidation of the TTF moiety resulted in disassembly of the polymer inclusion complex (PIC).