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Modèles chimiques du nitrure de carbone graphitique : lien structure-propriétés

Adrien Zambon 1
1 RICC - Reconnaissance Ionique et Chimie de Coordination
SYMMES - SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé : DRF/INAC/SYMMES
Abstract : Graphitic carbon nitride (gCN) is an organic semi-conductor which has lately attracted a lot of attention when its photocatalytic properties were highlighted for water splitting. It has been recently shown to be based on the heptazine core, but its three-dimensional structure remains elusive. This is first due to its poor solubility which prevents the use of classical characterization techniques, and second to the fact that changes in synthesis experimental conditions (precursors, temperature…) yield different materials. The synthesis of tailored and well-defined molecular models would therefore certainly be of great interest to better understand the structure-properties relationship of this material. This is the aim of the work presented in this manuscript. The reactivity of cyameluryl chloride, a monomeric precursor, has been studied, and a protocol for a quantitative selective substitution by aliphatic secondary amines has been determined. The use of deprotonation by a strong base or thermal treatment yielded two dimers and one linear trimer. The oligomers have been characterized by several technique (X-ray diffraction, NMR, IR, UV-vis absorption, emission, electrochemistry), and the obtained data were in close agreement to the ones observed in DFT. As a rule of thumb, a decrease of the electronic transition energies is observed for an increasing chain length. The application of extrapolation methods to the experimental data suggests that oligomers are relevant molecular models for gCN.
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Adrien Zambon. Modèles chimiques du nitrure de carbone graphitique : lien structure-propriétés. Chimie organique. Université Grenoble Alpes, 2015. Français. ⟨NNT : 2015GREAV024⟩. ⟨tel-01322358⟩

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