Thesis presented March 20, 2020

Abstract:
Graphitic carbon nitride (g-CN) 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 that the catalytic activity could be increased through metallic doping. However, the polymer's structure is not well known. Its poor solubility prevents the use of usual characterization techniques and the term g-CN includes a range of different compound, depending of the experimental conditions. The position of the metallic cation, its oxidation state and the interactions between the metal and the polymer are unknown. The determination of these interactions and the ability of the monomers (heptazines) to form inorganic complexes could help optimising/doping the material. This is the aim of the work presented in this manuscript. Heptazine based ligands have been developed and studied. The ability to coordinate transition metals have been studied and spectroscopic and electrochemical studies liked with DFT calculations helped to define the metal/ligand interactions. Generally, heptazines can be compared as soft bases and they behave as π-acceptor ligands. In parallel, it has been shown that heptazines have the ability to functionalize high specific surface area materials, such as graphene.

Keywords:
Heptazine, Transition metals, Complexes, g-CN

On-line thesis.