Well-controlled living polymerization of perylene-labeled polyisoprenes and their use in single-molecule Imaging.

graphical abstract
Granovic, G.T.; Csihony, S.; Bowden, N.B.; Hawker, C.J.; Waymouth, R.M.; Moerner, W.E.; Fuller, G.G.;
39, 8121-8127.

Functionalized perylene derivatives were synthesized with one or two alkoxyamine units. These compounds were used as initiators in the well-controlled living radical polymerization of isoprene, resulting in polymers with a perylene dye located at either the middle or end of the polymer. Using this approach, polyisoprenes were prepared with similar molecular weights, low polydispersities, and very good initiator efficiencies. Labeled chains were imaged on the single-molecule level in hosts of unlabeled polymer with similar composition. On the time scale from 0.2 to 2−5 s no difference between center- and end-positioned dyes was observed, suggesting that the dynamics outside of this time range should be studied. However, the most rigid host material led to the longest observed correlation times and the highest fraction of fluorophores that exhibited blinking behavior.