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Functional gold and silver complexes and supramolecules based on 9,10-diphenylanthracenes : photoactivity, catalysis and chiroptical properties

Abstract : This thesis describes the use of ligand design to achieve functional gold complexes for catalysis. Thioethers ligands were designed to form gold(III) chloride complexes which can be photoreduced to gold(I) using UV or visible light. Both gold species catalytically active lewis acids that can be used in a ‘one pot’ cascade cyclization reaction leading to a fused polyheteroaromatic compound. Functionalized phosphine ligands were also elaborated and the corresponding gold(I) chloride complexes smoothly grafted onto silica nano-objects for heterogeneous catalysis. Chiral induction from the chiral silica helices to the surface-bound gold complexes was confirmed using circular dichroism. In the presence of a silver salt, the covalently bound gold catalysts exhibited high reactivity and good recyclability in the dearomative spirocyclization reaction of aryl alkynoate esters. 9,10-Diphenylanthracene (DPA) based thioether ligands were also used to form silver complexes whose self-assembly can be tuned by the nature of the counteranion or by extending the length of the coordination chain. Their activity in homogeneous catalysis was confirmed in two tandem addition/cycloisomerization of alkynes using 0.5-1 mol% of catalytic loading. Based on the reversible covalent transformation of DPA upon cycloaddition of singlet oxygen, two systems demonstrating switchable properties were developed: a switchable [2+3] imine cage with three DPA pillars exhibiting an affinity for metal ions, and DPA-based chiral sulfoxides designed to exhibit tunable chiroptical properties.
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Zhen Cao. Functional gold and silver complexes and supramolecules based on 9,10-diphenylanthracenes : photoactivity, catalysis and chiroptical properties. Other. Université de Bordeaux, 2020. English. ⟨NNT : 2020BORD0142⟩. ⟨tel-03685187⟩

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