Ruthenium bipyridine poly

Schubert98 proposed the potential use of several ruthenium containing polymers in photovoltaic devices. A ruthenium containing poly(ethylene glycol) derivative 34 was synthesized by the functionalization of 4-(3-aminopropyl)-4-methyl-2,2-bipyridine with polyethylene glycol) (M =2800, PDI=1.05), which was activated with /V,/V-carbonyldiimidazole (Scheme 19)." Applications in solid electrolytes for DSSC was proposed. Polyester 35 was incorporated with... 

Meisel etal. [18-20] were the first to investigate how the addition of a polyelectrolyte affects photoinduced ET reactions. They found that charge separation was enhanced as a result of the retardation of the back ET when poly(vinyl sulfate) was added to an aqueous reaction system consisting of tris(2,2 -bipyridine)ruthenium(II) chloride (cationic photoactive chromophore) and neutral electron acceptors [21]. More recently, Sassoon and Rabani [22] observed that the addition of polybrene (a polycation) had a significant effect on separating the photoinduced ET products in an aqueous solution containing cir-dicyano-bis(2,2 -bipyridine)ruthenium(II) (photoactive donor) and potassium hexacyano-ferrate(III) (acceptor). These findings are ascribable to the electrostatic potential of the added polyelectrolytes. 

We report here studies on a polymer fi1m which is formed by the thermal polymerization of a monomeric complex tris(5,5 -bis[(3-acrylvl-l-propoxy)carbonyll-2,2 -bipyridine)ruthenium(11) as its tosylate salt,I (4). Polymer films formed from I (poly-I) are insoluble in all solvents tested and possess extremely good chemical and electrochemical stability. Depending on the formal oxidation state of the ruthenium sites in poly-I the material can either act as a redox conductor or as an electronic (ohmic) conductor having a specific conductivity which is semiconductorlike in magnitude. 

Much research has already been devoted in the past couple of years to (i) the immobilization of ATRP active metal catalysts on various supports to allow for catalyst separation and reycycling and (ii) ATRP experiments in pure water as the solvent of choice [62]. A strategy to combine these two demands with an amphiphilic block polymer has recently been presented. Two types of polymeric macroligands where the ligand was covalently linked to the amphiphilic poly(2-oxazo-line)s were prepared. In the case of ruthenium, the triphenylphosphine-functiona-lized poly(2-oxazoline)s described in section 6.2.3.2 were used, whereas in the case of copper as metal, 2,2 -bipyridine functionalized block copolymers were prepared via living cationic polymerization [63] of 2-methyl-2-oxazoline and a bipyridine-functionalized monomer as shown in Scheme 6.8. 

Functionalization of nanorods with polyelectrolytes has been carried out by layer-by-layer deposition (92). First, CTAB-coated nanorods are prepared. Since these nanorods are positively charged, they can adsorb cationic and anionic poly electrolytes. Functionalization of nanorods with dyes is possible a fluorescent dye, 4-chloro-7-nitrobenzofurazan has been functionalized on the surface of Ti02 nanorods (93). Functionalization with a photoactive molecule such as ruthenium(II) tris(bipyridine) is also possible (94). A thiol derivative of the bipyridyl complex (Ru(bpy)3+-Cs-SH) in dodecane thiol is used for the functionalization of gold nanorods. Functionalization of block magnetic nanorods is very useful (95), for example, in the separation of proteins. Consider a triblock nanorod consisting of only two metals, Ni and Au. If the Au blocks are functionalized with a thiol (e.g. 11-amino-1 undecane thiol) followed by covalent attachment of nitrostreptavidin, then one can... 

Poly bis(4,4 -tert-butyl-2,2 -bipyridine)-(2,2 -bipyridine-5,5 -diyl-[l,4-phenylene])- ruthenium(II)bishexafluorophosphate, poly bis(4,4 -tert-butyl-2,2 -bipyridine)-(2,2 -bipyridine-4,4 -diyl-[l,4-phenylene])- ruthenium(II)bishexafluorophosphate, poly bis(2,2 -bipyridine)-(2,2 -bipyridine-5,5 -diyl-[l,4-phenylene])- ruthenium(II)bishexafluorophosphate H,C sequence distribution 298... 

Many researchers have focused on the preparation and catalytic properties of polymer-bound ruthenium and osmium species because of their proven ability to catalyze homogeneous reactions and the vast synthetic chemistry available for their preparation. A series of preformed polymers of [M(bpy)2(pol)nCl]Cl, where M can be a Ru(II) or Os(II) metal center coordinated to 2,2 -bipyridine ligands (bpy) and anchored to a pyridine or imidazole nitrogen of a PVP or poly(N-vinylimidazole) polymer (pol), have been prepared and characterized with respect to charge transport rates and mechanisms in drop-coated films on electrode surfaces. Electrodes coated with films of the ruthenium polymer have been shown to mediate the oxidation of nitrite, and nickel bis(2-hydroxyethyl)dithiocarbamate. ... 

Wang HY, Xu GB, Dong SJ (2001) Electrochemilumineseenee of tris(2,2 -bipyridine)ruthenium(II) immobilized in poly(p-styrenesulfonate)-siliea-Triton X-100 composite thin-films. Analyst 126(7) 1095—1099. doi 10.1039/bl00376n... 

It has been reported that tris(2,2 -bipyridine)ruthenium(II) chloride catalyzed the photooxidative polymerization of diaryl disulfides by O2, by which poly(thioarylene)s were efficiently prepared. The polymerization proceeded through the electrophilic reaction of the sulfonium cation which was produced selectively by the photoredox system. The ruthenium(II) complex provided the first photocatalytic system for the polymerization of diphenyl disulfide. The linear structures of the obtained polymers were confirmed (32). 

As a matter of fact, the N-substitution induced in the polymer backbone a much weaker configurational flexibility than the 3-substitution. To circumvent this problem, Moutet et al. have synthesized polypyrroles N-substituted by ferrocene crown ether [270] and aza crown ether-linked bipyridine ruthenium (II) complexes [271]. Poly(19) was found to be Ba + and Ca " "-responsive [270], whereas the ruthenium(II)-based PPy was more sensitive to alkali metal cations [271]. The recognition of the cation binding was based on the changes in the electrochemical response of the metallic center instead of PPy. 

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