Ruthenium bipyridine poly metal

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... 

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. ... 

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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