Polymeric Ruthenium Complex Synthesis

Luminescent polymeric ruthenium tris(bipyridine) complexes have been studied extensively by our group as model inert metal systems.  We have investigated many polymerization mechanisms, cationic, anionic, ATRP and ROP, in combination with Ru metalloinitiators: Macroligand chelation and polymer coupling strategies have also been explored.  Numerous materials compositions—from hydrophobic polystyrenes, polyacrylates, and polyesters to water soluble poly(acrylic acid), poly(ethylenimine) to PEG—have been achieved for a wide range of homopolymer and block copolymer architectures.

Polymer architectures and block copolymers coming soon

See Publications for many studies featuring polymeric ruthenium tris(bipyridine) complexes.

Recent Work

Adapting polymeric ruthenium complexes for aqueous and biological applications has been the focus of recent work.  For example, ruthenium poly(2-ethyl-2-oxazoline) (Ru PEOX) was hydrolyzed to Ru polyethylenimine (PEI) and utilized in DNA entrapment, delivery, and transfection experiments.  Polymer effects on Ru luminescence properties were also investigated, indicating slower quenching relative to non-polymeric analogues.

Ru PEI scheme coming soon

“Ruthenium Tris(bipyridine)-centered PEI for Gene Delivery” Fiore, G. L.; Edwards, J. M.; Klinkenberg, J. L.; Payne, S. J.; Demas, J. N.; Gioeli, D. G.; Fraser, C. L. Biomacromolecules, 2007, 8, 2829-35.

In another study, a polymer coupling approach using Ru reagents with sulfur substituents in combination with activated PEG reagents was employed in the synthesis of Ru PEG targets.  Here too, polymer shell effects were noted, with slower quenching relative to non-polymeric Ru complex controls.

Ru PEG figure coming soon

“Ruthenium Tris(bipyridine) Complexes with Sulfur Substituents:  Model Studies for PEG Coupling” Fiore, G. L.; Goguen, B. N.; Klinkenberg, J. L.; Payne, S. J.; Demas, J. N.; Fraser, C. L. Inorg. Chem. 2008, 47, 6532-40.