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Synthesis of new tetrazines functionalized with photoactive and electroactive groups

Abstract : In this thesis, we have prepared different types of s-tetrazine derivatives for electrochemical and fluorescence studies. In the first part, we present a blibliographic study of s-tetrazine focussing on theirs synthesis and properties. In the second chapter, we introduce s-tetrazine derivatives as the ion pair receptor. These receprtors uses pi-anion type of interactions between ion pairs and s-tetrazines whcih has been seldom been observed in solution. The formation of complex between the ammonium salt (C8H17NH3Br or C8H17NH3I) and bis-s-tetrazine receptors is demonstrated by NMR and fluorescence titration experiments. It is also proved that receptor 82 binds stronger to ammonium salt than the shorter equivalents 80 and 81. Furthermore, all of them give the same unexpected selectivity order toward anions namely: I- > Br- > Cl-. Finally, a side reaction has been uncovered by UV-vis absorption which leads to the formation of Br2 or I2. Taking fully into account all spectroscopic results, we proposed a mechanism for this transformation. In the third part, in order to better understand the physico-chemcal properties of s-tetrazine, various s-tetrazines with different types of substituents have been prepared. It is clear that the electrochemical properties of the tetrazine nucleus depend on the electron affinity of its substituent and not on the size. Furthermore, electron donor groups quench the fluorescence of s-tetrazine even if they are not directly linked. A new type of s-tetrazines has been obtained through an unexpected reactivity of chloro-s-tetrazine. This reaction could give unsymmetrical s-tetrazines bearing one heteroatom and one alkyl chain which is useful for future developmemt of their properties. In the last part, we talk about new s-tetrazine dyads with improved brightness. Based on energy transfer from a donor part (naphthalimide or benzimidazole) to an acceptor core (tetrazine), these compounds own good fluorescence quantum yields, longer lifetimes and higher brightness. One derivative has been used to prepare a three colors fluorescent and electrochemically switchable device.
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Qing Zhou. Synthesis of new tetrazines functionalized with photoactive and electroactive groups. Other. École normale supérieure de Cachan - ENS Cachan, 2012. English. ⟨NNT : 2012DENS0039⟩. ⟨tel-00796461⟩

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