Multi-armed, TEMPO-functionalized unimolecular initiators for starburst dendrimer synthesis via stable free radical polymerization. 1. Tri azo-functionalized unimer

The synthesis of azobenzene-functionalized multi-armed unimolecular initiators or "unimers" that can be polymerized using styrene or styrenic derivatives via TEMPO (2,2,6,6-tetramethylpiperidenyl-1-oxyl) mediated stable free radical polymerization (SFRP) is described. The unimers are composed of an azobenzene-functionalized core and a TEMPO-modified unit. Homopolymers and copolymers of styrene and acetoxystyrene were synthesized using the mono-and trifunctionalized unimers as initiators under bulk conditions with average molecular weights and polydispersities reported. The studies lay the groundwork for further investigations involving SFRP towards building a light harvesting system by introducing chromophores onto the polymer chains for capturing light and thence transferring it to the azobenzene core.