Search results for "Porphyrine"
showing 9 items of 9 documents
Inter- and Intramolecular Anodic Nucleophilic Substitutions of Porphyrins. Reactivity of the resulting products
2020
This manuscript presents the functionalization of porphyrins by anodic nucleophilic substitution (SNAn). After an introduction describing generalities on porphyrin, the 2nd chapter deals with the 2-step synthesis of primary aminoporphyrins. The 1st electrochemical step consists in oxidizing the porphyrin at the 1st oxidation potential in the presence of pyridine. The formed pyridinium-porphyrin is then transformed into an amine by opening the pyridinium fragment by nucleophilic attack of piperidine.The 3rd chapter presents the synthesis and redox reactivity of porphyrins substituted with one (or several) aromatic groups carrying an imine function (thiopyrimidine, quinoline and aminopyridine…
Porphyrines et tétraazamacrocycles dérivés du DOTA : association de deux ligands pour la chélation de métaux d'intérêt en imagerie médicale multimoda…
2012
The goal of my PhD thesis was to synthesize new molecules, which give access to heterobimetallic complexes with interesting properties for multimodal imaging. In this manuscript, several main points have been studied. The first part of this work concerns the synthesis and characterization of ligands. We describe here the synthesis of five new ligands based on the association of one porphyrin and one or several cyclen derivatives. Those ligands are water-soluble. During the synthesis, we have targeted improvements to our work and developed a new synthetic pathway, which allowed us to obtain one ligand incorporating a porphyrin, a cyclen derivative and a free amine function. This function cou…
Electrochemical reactivity of magnesium porphine : functionalization, oligo-polymerization and application to the synthesis of porphyrins and multi-p…
2012
This work deals with the redox reactivity of magnesium porphine, the study of its electropolymerization and resulting materials, of its functionalization by nucleophiles as well as the mechanistic investigation of the C-C oxidative coupling on a tris-meso-substituted porphyrin model.The electrochemical oxidation of magnesium porphine to its cation radical leads to oligomers in solution and polymers on the electrode, which molecular structure depends on the imposed potential. The reactivity of the cation radical has also been exploited by adding sufficient amount of nucleophiles (pyridine and triphenylphosphine) in the reactional in order to inhibit the oligomerization/polymerization process…
PI-Extension of porphyrins via intramolecular aromatic oxidative C-N coupling
2019
Π-extension of porphyrins has been performed via intramolecular oxidative C-N coupling of peripheral pyridinyl fragment(s) with the porphyrin core. These fusion reactions lead to the formation of C-N bond(s) between the substituent(s) and the porphyrin. The precursors were functionnalized with 2-mercaptopyridine, 8-hydoxyquinoline and 2-picoline at their meso or β-pyrrolic positions via aromatic nucleophlic substitution, cross-coupling reaction or reaction of the macrocycle with organolithium reagents. Voltametric analyses revealed some marked differences on the reactivity of the porphyrins depending on their substitution pattern and metalation (nickel(II) or zinc(II)). Chemical and electro…
Synthèse de nouveaux agents bimodaux hydrosolubles pour l'IRM, l'imagerie nucléaire, l'imagerie biphotonique et la génération de second harmonique
2015
The goal of my PhD studies was to synthesize new compounds for possible medical imaging applications. The first part of my thesis focused on the synthesis of heteroleptic ligands to achieve the chelation of two different metals aimed at addressing two types of medical imaging. We first synthesized porphyrins, which are well-known for the chelation of numerous transition metals. We focused on copper, whose copper-64 isotope is a β+ emitter usable in Positron Emission Tomography (PET). These porphyrins have been coupled with a DOTA derivative. This molecule, metallated with gadolinium, is well-known in Magnetic Resonance Imaging (MRI). Our compounds display encouraging relaxivities for MRI ap…
Self-cleaning materials active in the visible range based on porphyrin-sensitised titanium dioxide
2016
In the last decades, nanostructured semiconductors played a central role in the material science scene because of their numerous applications spanning from renewable energy to organic/hybrid electronics up to photocatalysis. Titanium dioxide is one of the most used semiconductors because of its low cost, chemical stability, sustainability and versatility. Indeed, it is widely employed as photo-active or charge- transporting material in electronic devices, as photocatalyst in water de-pollution treatments etc.. Remarkably, one of the most interesting application of titanium dioxide consists of the protection and conservation of cultural heritages. Actually, TiO2 photocatalytic properties are…
Visible light active self-cleaning materials based on porphyrin-sensitised titanium dioxide
2017
Starting from second half of last century, nanostructured semiconductors have had a crucial function in the material science because of their wide application field going from renewable energy to organic/hybrid electronics up to photocatalysis. Among those materials, titanium dioxide is probably the most used because of some important characteristics like the chemical/mechanical stability, environmental sustainability, its low cost and versatility. Indeed, it has been successfully employed as photo- and electro-active component in electronic devices as well as photocatalytic agent1 in water de-pollution application. Interestingly and importantly together, titanium dioxide may also be applie…
Fluorescent organometallic complexes : when the photovoltaic leads to theranostics
2013
The goal of my PhD thesis was to synthesize new molecules, which give access to fluorescentorganometallic complexes with interesting properties for photovoltaic and theranostic. In thisproject, several main points have been studied.The first part of this manuscript concerns the synthesis of new metallocene and metalloporphyrinsbasedorganometallic complexes to the design of solar cells. After a short introduction, wepresented the synthesis of titanium complexes and metalloporphyrins in the first chapter. Inparticular, we described the synthesis of model compounds and the difficulties encountered duringthe transition to porphyrin derivatives. However, in view of results obtained and opportuni…
Functionalised Imidazoporphyrins and their application in catalysis
2017
A broad series of functionalized imidazo[4,5-b]porphyrins was synthesized by the acid-catalyzed condensation of 2,3-dioxo-5,10,15,20-tetraarylchlorins with aromatic aldehydes. Both steric and electronic features of meso-aryl substituents influence on the product yield ranging from 18% to 90%.Single-crystal X-ray diffraction analysis of the structure of zinc(II) 5,10,15,20-tetramesityl-2-(4-pyridyl)-1H-imidazo[4,5-b]porphyrinate showed that this compound forms 1D coordination chains in the solid state.The post-synthetic modifications of imidazo[4,5-b]porphyrins were investigated by performing the Suzuki-Miyaura coupling reaction, preparing water-soluble imidazoporphyrins and linear/angular b…