Novel hybrid materials, based on polymeric ruthenium complexes, have been synthesized and characterized. The preparation of a new vinylic tris(bipyridine)ruthenium complex in high yields enabled the synthesis of soluble polymeric materials with high metal loading, using a controlled polymerization technique such as atom transfer radical polymerization. Moreover, combination of this monomeric complex with other monomers, known for their electron or hole transporting properties, led to soluble copolymers of various desired ruthenium loadings. Characterization of the synthesized polymers and copolymers was performed using NMR, SEC, and viscometry. The polymer-metal hybrid materials' optical properties were studied in detail through UV-vis and photoluminescence spectroscopies, showing the [Ru II (bpy) 3 ] complexes' intense optoelectronic characteristics, also in combination with the optical properties of the oxadiazole or carbazole units in the copolymer case.

Semiconducting oligomers and polymers decorated with two or one dendronized tpy‐Ru(II)‐tpy metallocomplexes are presented. Initially, free terpyridine end‐functionalized semiconducting oligomers (distyrylanthracene, quinquephenylene, mono‐ and trifluorenes) were prepared while in a second approach, atom transfer radical polymerization was employed for the preparation of side‐chain oligomeric and polymeric (oxadiazole)s using a terpyridine initiator. These terpyridine‐bearing oligomers and polymers were complexated with a Percec‐type first‐generation (G1) dendronized terpyridine–Ru(III)Cl3 monocomplex, having two dodecyloxy groups. All oligomeric and polymeric metallocomplexes were characterized via NMR spectroscopies for their structural perfection and via UV‐Vis and PL spectroscopies for their optical properties. The existence of the organic semiconducting blocks in combination with the terpyridine–Ru(II)–terpyridine groups afforded hybrid metallo‐semiconducting species presenting the optical features of both their components. Moreover, their thin‐film morphologies were investigated through atomic force microscopy, revealing, in some cases, an organization tendency in the nanometer scale. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1939–1952, 2009