Conception of organic capsules by self-organization of functionalized heterocycles

Abstract : This work deals with the synthesis and characterization of new electron-rich discrete molecular cages, prepared via the coordination-driven self-assembly methodology, as well as on evaluating their redox and host-guest properties. The general concepts guiding the metal-driven self-assembly methodology are presented. Three types of redox-active tetratopic ligands (L) featuring either a tetrathiafulvalene (TTF), a dithiol-fluorene (DTF) or a π-extended tetrathiafulvalene (exTTF) have been designed. Their ability to generate self-assembled cages upon combination with various metal complexes (M) has been studied. In the first case, M8L2 metallacages were obtained, whose geometry offers a unique opportunity to promote close inter-TTF interactions upon oxidation, as confirmed through electrochemical studies as well as from single-crystal DRX from an electrocrystallized oxidized salt. In the second case, several discrete self-assemblies MxLy (cages, clips) were obtained and characterized from new electro-active ligands based on the 9-(1,3-dithiol-2-ylidene)fluorene (DTF) unit. Their redox properties as well as their binding ability towards electro-deficient planar species show a strong dependence to the self-assembly geometry. Considering the exTTF ligand, large (ca. 4000 Å3) electroactive M12L6 metallacages were obtained from combining with trans palladium or silver complexes. Le latter exhibits a disassembling process upon oxidation, giving rise to an unprecedented redox-triggered transformation of discrete metalla-cage into a coordination polymer. Finally, a new benzo[1,2-b:4,5-b'] dithiophene aromatic scaffold is investigated as an alternative π-extended electron-rich derivative. The critical role of non-covalent 1,5 S···S interactions is demonstrated by a combined experimental and theoretical approach.
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Serhii Krykun. Conception of organic capsules by self-organization of functionalized heterocycles. Organic chemistry. Université d'Angers; Kiïvsʹkij nacìonalʹnij unìversitet imeni Tarasa Ševčenka (Ukraine), 2019. English. ⟨NNT : 2019ANGE0007⟩. ⟨tel-02307126⟩

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