Ruthenium complex polymers metallized films

Subsequent to isolation of the polymer, the metallization could be conducted in a similar manner as that of the complexes reported elsewhere for DCH-Ru complexes (27-28). The ruthenium complex polymers, shown in Figure 2, thus made would be expected to exhibit similar electrochromic properties as the dinuclear ruthenium complexes while possessing the film forming characteristics of the parent polymer. We report herein the synthesis and characterization of these polymers. 

A recent development31 is the preparation of metal polymer complexes directly on the electrode via the electrochemically induced polymerization of the metal complex. Ruthenium(II) and osmium(II) complexes with ligands containing aromatic amines, e.g. 3- or 4-aminopyridine or 5-amino-1,10-phenanthroline, are electrochemically polymerized to yield a film of the metal polymer on the electrode surface. The polymerization involves free radicals, which are formed via the initial oxidation of the metal complex to a radical cation and subsequent reaction of the radical cation with a base to yield the free radical. 

Abstract Pressure-sensitive paint (PSP) is applied to the areodynamics measurement. PSP is optical sensor based on the luminescence of dye probe molecules quenching by oxygen gas. Many PSPs are composed of probe dye molecules, such as polycyclic aromatic hydrocarbons (pyrene, pyrene derivative etc.), transition metal complexes (ruthenium(II), osumium(II), iridium(III) etc.), and metalloporphyrins (platinum (II), palladium(II), etc.) immobilized in oxygen permeable polymer (silicone, polystyrene, fluorinated polymer, cellulose derivative, etc.) film. Dye probe molecules adsorbed layer based PSPs such as pyrene derivative and porphyrins directly adsorbed onto anodic oxidised aluminium plat substrate also developed. In this section the properties of various oxygen permeable polymer for matrix and various dye probes for PSP are described. 

The electropolymerization method of functional monomers has proved successful in many cases, in particular to incorporate various ligands and their metallic complexes, like salen [66,245], porphyrin [246], diphosphine [247], pyridine [71,80,248,249], crown ether [250,251], metallofullerene [252], tetraazacyclotetradecane [253], or Prussian blue type [254] in a conjugated organic material like PPy, PTh, or PANE Thick films are likely to be obtained provided that the polymer is redox active at the deposition potential due to this, Zotti et al. demonstrated that 5,5 -bis(3,4-(ethylenedioxy)thien-2-yl)-2,2 -bipyridine could be electropolymerized when complexed by iron and ruthenium, but not in the case of complexation by nickel or copper [71]. 

Polymers whose backbones consisted solely of metal-metal bonds have been synthesized by electrochemical reduction of ruthenium and osmium complexes (47,48). Reduction of [M Htra s-Cl2)(bipy)(CO)2] (M = Ru, Os) (24) to M° complexes generated a polymeric film (25) following loss of the trans chloride ligands (48) (eq. 8). Both the ruthenium- and osmium-based coordination polymers were selective for the reduction of carbon dioxide. 

In the latter example and others involving polypyrrole films electroformed from a complex between a transition metal (Ru(II)) and a bi- or terpyridine-substituted pyrrole [201, 202], the electron self-exchange was ensured by either the viologen or Ru(II) units and not by the polymer. As a matter of fact, the PPy matrix was undoped when poly(3) was used for electrocatalytic reduction experiments or overoxidized when the films containing ruthenium(II)-based complexes were involved in oxidation experiments [201, 202]. 

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