Synthesis and properties in solution of ruthenium(II) coordination polymers

Abstract

Synthetic strategies are presented for the preparation of readily soluble ruthenium(II) coordination polymers of high molecular weight. The constitutional homogeneity of the polymers is proved using high‐resolution NMR spectroscopy, and their molar masses are estimated from 1H NMR spectra, viscosity data and SAXS investigations. The polymers are shown to be conformationally rigid, and to form either densely packed coils or rods. It is mainly this difference in shape which causes the very specific properties of the respective polyelectrolytes in the solid state as well as in dilute solution. Finally, the UV‐vis absorption spectra of some of these materials are presented.

Soluble dynamic coordination polymers as a paradigm for materials science

“…This linear arrangement is due to the octahedral coordination geometry of the metal. However, the ditopic ligand must be rigid enough to prevent ring formation; otherwise lower molecular weight species will be favored due to entropic reasons [46].…”

Ruthenium Bipyridine-Containing Polymers and Block Copolymers via Ring-Opening Metathesis Polymerization

“…A number of ruthenium diimine-containing polymeric materials, containing the ruthenium moiety in either the polymer main chain or the side chain, have been reported in the literature . For example, polymers based on polystyrene, polypyrroles, π-conjugated poly(2,2‘-bipyridine-5,5‘-diyl), poly(vinylbipyridine), polyesters, poly(1-vinylimidazole), poly( p -phenylenevinylene) with pendant terpyridine, electropolymerized bipyridine or terpyridine derivatives, and metallo-supramolecular block copolymers have been generated. Star polymers with ruthenium−polypyridine complexes in the core or on branches have been prepared.…”

An “Attachment Through Coordination” Approach to Side Chain Dendritic Polymers

“…Such behavior has been reported for various coordination polymers containing tpy-Ru II -tpy groups and can be explained in terms of the polyelectrolytic nature of the polymers due to the presence of the Ru II and their counterions. [14] Attempts to reduce the polyelectrolyte repulsion and obtain true viscosity values by means of intrinsic viscosity were also made, by addition of NH 4 PF 6 to the DMSO solutions, but even a 10 mm salt concentration caused the polymeric complex to precipitate from the solution. In any case, these observations alone demonstrate the different nature of the dendronized polymeric complexes with respect to the uncomplexed polyether precursors.…”