Carboxyl and ethynyl-substituted dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, properties, and applications

Wang, Yunfei (2015) Carboxyl and ethynyl-substituted dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, properties, and applications. Masters thesis, Memorial University of Newfoundland.

[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.

Download (9Mb)

Abstract

This thesis describes a systematic study of new dithiafulvene (DTF) and tetrathiafulvalene vinylogue (TTFV) derivatives as redox-active π-conjugated molecular materials. The content of this thesis work is divided into two major parts. In the first part, a series of carboxylate ester and carboxyl-substituted DTFs and TTFVs were synthesized and their electronic and electrochemical redox properties were characterized by UV-Vis spectroscopic and cyclic voltammetric analyses. The carboxyl-TTFV was applied as a redox-active ligand to complex with zinc ions, forming a stable Zn- TTFV coordination product. The structural, electrochemical, and thermal properties of the coordination product were investigated by infrared spectroscopy, powder X-ray diffraction, cyclic voltammetry, and differential scanning calorimetric analyses. Furthermore, the microscopic morphological and porosity properties of the Zn-TTFV coordination product were measured by scanning electron microscopy and nitrogen gas adsorption experiments. In the second part, a series of ethynyl-substituted DTF regioisomers was synthesized and then used as starting materials to construct further π-extended derivatives through oxidative dithiafulvenyl coupling and Cu-catalyzed alkynyl homocoupling reactions. The resulting π-conjugated systems were subjected to UV-Vis absorption and cyclic voltammetric analyses to examine their electronic properties and redox reactivity. Based on the characterization studies, a understanding of the structure-property-reactivity relationships for these compounds has been established.

Item Type: Thesis (Masters)
URI: http://research.library.mun.ca/id/eprint/12221
Item ID: 12221
Additional Information: Includes bibliographical references (pages 78-85).
Keywords: Dithiafulvenes, Tetrathiafulvalene vinylogues, Coordination polymers, Conjugated materials
Department(s): Science, Faculty of > Chemistry
Date: November 2015
Date Type: Submission
Library of Congress Subject Heading: Tetrathiafulvalene--Synthesis; Tetrathiafulvalene--Properties; Vinyl polymers--Synthesis; Vinyl polymers--Properties

Actions (login required)

View Item View Item

Downloads

Downloads per month over the past year

View more statistics