Luminescent polymeric ruthenium complexes with polystyrene‐b‐poly(methyl methacrylate) macroligands: The sequential activation of initiator sites for blocks generated by parallel polymerization mechanisms

The synthesis of polystyrene‐b‐poly(methyl methacrylate) diblock copolymers with a luminescent ruthenium(II) tris(bipyridine) [Ru(bpy)₃] complex at the block junction is described. The macroligand precursor, polystyrene bipyridine‐poly(methyl methacrylate) [bpy(PS–H)(PMMA)], was synthesized via the atom transfer radical polymerization of styrene and methyl methacrylate from two independent, sequentially activated initiating sites. Both polymerization steps resulted in the growth of blocks with sizes consistent with monomer loading and narrow molecular weight distributions (i.e., polydispersity index < 1.3). Subsequent reactions with ruthenium(II) bis(bipyridine) dichloride [Ru(bpy)₂Cl₂] in the presence of Ag⁺ generated the ruthenium tris(bipyridine)‐centered diblock, which is of interest for the imaging of block copolymer microstructures and for incorporation into new photonic materials. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4250–4255, 2002