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Ruthenium-containing polymers-synthesis, characterisation and electrochemical properties

Geraty, Suzanne M (1989) Ruthenium-containing polymers-synthesis, characterisation and electrochemical properties. PhD thesis, Dublin City University.

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In this work, the synthesis and characterisation of a series of ruthenium-containing metallopolymers based on poly-H-vinylimidazole are reported, with a view to subseguently investigating their electrochemical properties and potential applications of electrodes modified with these polymers. The prepared complexes were characterised using spectroscopic and electrochemical techniques. It was found that the products, or ratios of products, obtained depended on the reaction conditions, i.e. polymer:metal ratios, reflux time and reaction solvent. The two main products obtained were of the from [Ru (bipy) 2 (PNVI) Cl ] ’r and [Ru(bipy} 2 (PNVI) 2 ] > The electrochemical properties of these materials were examined as films on the surface of glassy-carbon electrodes. Sweep-rate dependence, electrolyte dependence and film stability were subsequently studied. The electrochemical response was found to depend strongly on the nature of the supporting electrolyte. Glassy-carbon electrodes coated with methanolic solutions of [Ru(bipy) n (PNVI'Cl] and fRu(bipy)(PNVI) 2 ] were used to study the photochemical properties of these materials. Electrolyte dependence was again found to be very significant,, both as a function of the reaction product and as a function of film stability. [Ru.(bipy) ( PNVI) Cl]was found to exhibit interesting phor.ochem.rcal properties, particularly in sulphatebased electrolytes where a photostable sulphate intermediate complex was found to form. This lends possibilities to potential applications in switching devices. The photoresponsive properties of [ Ru(bipy) 2 (PNVI) p ] have also been investigated in the presence of' suitable external quenchers. The diffusion co-efficient of the electron in the film was investigated using the technique of chronoamperometry. The charge-transport diffusion coefficient was determined to be of the order of 10’ cm s' . The mediating properties of the monosubstituted complex were studied. This complex v/as found to catalyse the oxidation of Fe(II) to Fe (III) is aqueous solution. Two substrates, (NH^)2Fe(SO) 2 and K^Fe(CN)g were studied for this purpose. ^ Electrolyte and film thickness were found to be important features in the results obtained for these studies. All results obtained were compared to similar results previously obtained for polyvinylpyridine based analogues.

Item Type:Thesis (PhD)
Date of Award:1989
Supervisor(s):Vos, Johannes G.
Uncontrolled Keywords:Ruthenium; Polymers
Subjects:Physical Sciences > Electrochemistry
DCU Faculties and Centres:DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences
Use License:This item is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 3.0 License. View License
ID Code:18747
Deposited On:30 Jul 2013 11:42 by Celine Campbell. Last Modified 30 Jul 2013 11:42

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