Conjugated metallopolymers containing 2,2'-bithiazole

MacLean, Brian (2002) Conjugated metallopolymers containing 2,2'-bithiazole. Doctoral (PhD) thesis, Memorial University of Newfoundland.

[img] [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 (20Mb)
  • [img] [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

Ruthenium and osmium conjugated metallopolymers containing a bithiophene-co-bithiazole backbone have been synthesized and their electrochemistry investigated. This relatively new class of materials has demonstrated enhanced rates of charge transport relative to redox metallopolymers in which a saturated organic network connects pendant metal complexes. Applications requiring fast electrochemistry, such as molecular switching and electrocatalysis, clearly can benefit from this enhancement. -- Electropolymerization from boron trifluoride dethyletherate (BF₃ OEt₂) permitted facile deposition of polymer films for electrochemical experiments. Impedance spectroscopy has been used to investigate electron transport rates in these metallopolymers. DcCM² was found to be over 20 times greater in poly-[Ru(5,5'-bis(2-thienyl)-2,2’-bithiazole)(bpy)₂³⁺/²⁺] than in poly-[Ru((6,6'-bibenzimidazole-2,2’-diyl)-2,5-pyridine)(bpy)₂³⁺/²⁺] as a result of better energy matching of the ruthenium t₂g orbital with the HOMO band in the poly[5,5'-bis(2-thienyl)-2,2'-bithiazole] backbone. A hole-type mechanism of superexchange is proposed for this system.

Item Type: Thesis (Doctoral (PhD))
URI: http://research.library.mun.ca/id/eprint/1208
Item ID: 1208
Additional Information: Bibliography: leaves 182-188.
Department(s): Science, Faculty of > Chemistry
Date: 2002
Date Type: Submission
Library of Congress Subject Heading: Metal-filled plastics; Bioconjugates

Actions (login required)

View Item View Item

Downloads

Downloads per month over the past year

View more statistics