Synthesis of Terpyridine-Terminated Polymers by Anionic Polymerization

The synthesis of terpyridine-functionalized polystyrene was achieved by reacting 4‘-chloro-2,2‘:6‘,2‘ ‘-terpyridine (terminating agent) with “living” polymeric carbanions synthesized by anionic polymerization. The obtained polymers were characterized by gel permeation chromatography, nuclear magnetic resonance, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, elemental analysis, and ultraviolet−visible absorption spectroscopy. The conversion of the polystyryllithium species into the corresponding 1,1-diphenylalkyllithium chain ends by reaction with 1,1-diphenylethylene (DPE) was a necessary step in order to promote an efficient chain-end functionalization and to avoid undesired side reactions (coupling) between the polymer chains due to the high reactivity of the polystyryl anion. Moreover, the obtained well-defined terpyridine-terminated polystyrenes were used for the synthesis of self-assembled metallo-supramolecular block copolymers.