Synthesis and Properties in Solution of Rodlike, 2,2‘:6‘,2‘ ‘-Terpyridine-Based Ruthenium(II) Coordination Polymers

Abstract

Rodlike ruthenium(II) coordination polymers have been prepared via the conversion of 4,4′′bis(2,2′:6′,2′′-terpyridine)-2′,5′-dihexyl-p-terphenyl and an appropriately reactive ruthenium(III) species in 1-butanol/DMA. The diamagnetic polymers readily dissolve in polar organic solvents, and their homogeneous constitution could thus be proven and their degrees of polycondensation could be estimated to be Pn g 30, using 1 H and 13 C NMR spectroscopy. The Pd-catalyzed polycondensation of bis[4′-(pbromophenyl)-2,2′:6′,2′′-terpyridine]ruthenium(II) tetrafluoroborate and 2,5-dihexylbenzene-1,4-diboronic acid, on the other hand, which should lead to a constitutionally identical polymer, only resulted in oligomers under all tested conditions. The intrinsic viscosity [η] of the high-molecular-weight polymers (determined in 0.02 M NH4PF6/DMA) is of the order of 300 mL g -1 . In salt-free DMA solution and thus at low ionic strengths, the polymers display the characteristic polyelectrolyte behavior in viscosity experiments which becomes more and more pronounced with increasing Pn. The UV-vis absorption spectra recorded in DMA solution do not show any evidence of intramolecular electronic interactions of the metal centers along the polymer chains: on the contrary, the coordination polymers behave like sequences of electronically independent ruthenium(II) complexes.

From Ruthenium Complexes to Novel Functional Nanocomposites: Development and Perspectives

“…The first direct synthesis of a polymer containing a transition metal complex gave rise to a coordination polymer based on ruthenium(II)-terpyridine complexes. [16,17] The combination of conventional polymers to metal centers generates intrinsic properties of the metal, retaining the properties of the conventional polymer. A new property acquired due to the metal center, is the electroactivity amongst all the transition metals, and the ruthenium has been widely used by coordination chemists mainly due to its ease of forming extremely stable complexes, especially with pyridine ligands and their derivatives.…”

Synthesis of rodlike ruthenium(II) coordination polymers having metal-nitrogen and metal-carbon bonds in their main chains

“…This decision was made on the basis of recent work, where we prepared rodlike coordination polyelectrolytes 1 (Scheme 1) [19]. The rodlike shape of these polymers was achieved because the two 2,2':6',2''-terpyridine moieties of ligand monomer 2 are connected by an all-para linked terphenylene bridging unit.…”

“…Moreover, they are key compounds at the borderline of macromolecular and supramolecular science. When readily soluble in conventional solvents and rod-like in shape, for example, they are fascinating self-organizing buildingblocks for multilayer systems [12,13] as well as important models for developing a profound understanding of polyelectrolyte behavior in solution [19]. Also, they seem to have a potential in fields like artificial photosynthesis, solar energy conversion and catalysis.…”

Synthesis, Characterization and Coordination Behavior of Zinc Supramolecular Polyurethane End-Capped with Terpyridine

“…In addition to hydrogen bonding units, [4] metal-ligand interactions have mainly been utilized [5,6]. As a result, linear high-molar-mass polymers [7][8][9][10][11], defined block co-polymers [12,13], star-like systems [14][15][16][17], graft co-polymers [18] and micelles [19], as well as networks [20] have been reported.…”