Dithiolene based conjugated metallopolymers

Kean, Christopher L. (2001) Dithiolene based conjugated metallopolymers. Masters thesis, Memorial University of Newfoundland.

[English] PDF (Migrated (PDF/A Conversion) from original format: (application/pdf)) - Accepted Version Available under License - The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. Download (17MB) [English] PDF - Accepted Version Available under License - The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. (Original Version)

Abstract

Incorporation of metals into conjugated organic polymers is a relatively novel concept, and offers promise for the development of advanced electronic, catalytic and sensing materials. Dithiolene complexes are attractive building blocks for such systems since they exhibit superconductivity and have been shown to display interesting non-linear optical properties. Also, their aromaticity provides for facile n-doping. -- This project entails the synthesis of several monomeric nickel dithiolene complexes having peripheral thiophene moieties. These thiophene units permit electropolymerization of these complexes to yield metallopolymers which have 100% coordination of a metal center. Redox properties of both complexes and polymeric films were characterized by cyclic voltammetry. Also described is the further characterization of poly(bis[1,2-di(2-thienyl)-1,2-ethenedithiolene]-nickel) by electronic absorption, spectroelectrochemistry and conductivity measurements. The later were accomplished by impedance spectroscopy and interdigitated microsensor electrodes. The conductivity of poly(bis[1,2-di(2-thienyl)-1,2-ethenedithiolene]nickel) was determined to be 10-6 S cm-1 and 10-4 S cm-1 at +0.2 V and +1.0 V respectively. It is anticipated that further optimization of film growth procedures will lead to an increase in these conductivities.

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