Electrochemical Studies of Redox-Active, π-Conjugated Molecules: Development of Molecular Sensors, Tectons for Self-Assembly, and Conducting Materials

Cecilie Lindholm-Fleige

Abstract

The aim of this thesis has been to elucidate how the redox properties of p-conjugated molecules can be finely tuned by structural modifications. The work has focused on derivatives of tetrathiafulvalene, ttf (electron donors), cyclic and acyclic acetylenic scaffolds (electron acceptors), azulene (electron acceptors), and various oligo(hetero)acene- extended derivative of ttf. The redox properties have been studied to develop molecular sensors as well as new redox-controlled tectons for supramolecular chemistry, i. E. Species that undergo associations upon oxidation. The thesis is divided into five chapters. Chapter 1 gives a general introduction to organic redox systems and the methods used for studying them. In chapter 2, i present studies on tetraethynylethene, tee, scaffolds. A particular focus is on so-called radiaannulenes, tee-based macrocycles, which can be seen as small fragments of 6,6,12- graphyne (see example of structure in the figure below, a). These molecules underwent particularly easy reductions, which is explained by a gain of aromaticity upon reduction, which was supported by calculations. In chapter 3, i present studies on a series of azulene derivatives (see structure in the figure below, b). Electrochemical data could here nicely be correlated with calculated redox potentials. In chapter 4, i show how ttfpyridine conjugates (see example of structure in the figure below, c) can be employed to selectively detect various metal ions. In chapter 5, i show how the redox properties of indenoflurene-extended ttfs (see example of structure in the figure below, d) can be tuned by introduction of thiophene rings in the oligoacene core. The radical cations underwent associations depending on the size and planarity of the p-system
Original languageEnglish
PublisherDepartment of Chemistry, Faculty of Science, University of Copenhagen
Publication statusPublished - 2018

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