Synthesis and Studies of Novel π-Conjugated Chromophores: Subphthalocyanines, Rhodamines and Oligo(phenyleneethynylene)s

Henriette Schjøtt Lissau

Abstract

This ph. D. Thesis describes the synthesis and studies of novel -conjugated chromophores based on the subphthalocyanine dye, the rhodamine fluorophore and an oligo(phenyleneethynylene) molecular wire. The main part of the thesis relates to different aspects of subphthalocyanines, which is described in chapters 1-4, while chapter 5 relates to the rhodamines and chapter 6 to oligo- (phenyleneethynylene)s with thioacetate end-groups. Chapter 1: gives an introduction to -conjugated chromophores, in particular, subphthalocyanines, including their discovery, functionalizations, and various scaffolds, in which the subphthalocyanines can be incorporated. Chapter 2: reveals different types of functionalization of the subphthalocyanines, including axial and peripheral substitution, along with a -conjugated extension of the periphery, generating novel subporphyrazines. A novel subporphyrazine with a chlorinated acenaphthylene moiety fused into the periphery was prepared and the uv-vis absorption studies revealed that it is a strong light-harvester. Chapter 3: describes the synthesis and design of a novel subphthalocyanine-functionalized radiaannulene. Uv-vis absorption studies reveal that the subphthalocyanine scaffold is a remarkably strong light-harvester, and electrochemical studies reveal that it is a multi-electron acceptor undergoing several reversible reductions. Chapter 4: concerns the synthesis and optical properties of ruthenium -complexed subphthalocyanines, together with attempts of incorporating an electron-donating 1,1,4,4-tetracyanobuta-1,3- diene (tcbd) unit. Chapter 5: presents synthesis and optical properties of a monomeric and a series of homodimeric rhodamines, along with the preliminary forster/fluorescence resonance energy transfer (fret) measurements in the gas phase. Chapter 6: relates to the synthesis of novel acceptor-acceptor (a-a) cruciforms with either formyl or malononitrile acceptors orthogonally placed at an oligo(phenyleneethynylene) wire. Conducting probe atomic force microscopy measurements on self-assembled-monolayers (sam) revealed a strong influence of the donor-acceptor functionalization on the conducting properties. Unfortunately, the conducting properties of the a-a cruciforms were not measured due to a poor quality of the sam.
OriginalsprogEngelsk
ForlagDepartment of Chemistry, Faculty of Science, University of Copenhagen
StatusUdgivet - 2017

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