Nouvelles versions organométalliques du polyaniline contenant des dérivés substitués de quinone diimine, para-diaminebenzène, anthraquinone diimine et 9,9'- anthracènediamine pour des applications photoniques
Other titre : New organometallic versions of polyaniline built upon substituted derivatives of quinone diimine, para-diaminebenzene, anthraquinone diimine and 9,9'- anthracenediamine for photonic applications
In the last few decades, research in the field of organometallic polymers has been in rapid expansion. The most notable applications are certainly photonic devices such as solar cell and light emitting diode. This master's thesis comprises four experimental sections. The first section reports the synthesis and characterization of organometallic polymers containing the trans-platinum(II) di-yne bisphosphine building blocks and substituted derivatives of quinone diimine and benzenediamine along with the corresponding model compounds. This work will be submitted to Inorganic Chemistry for publication. Indeed, these new assembling building blocks (Chapter 2 ) will served as ligands and exhibit the following structures: H-C[xi]C-C[subscript 6]H[subscript 4]-N=C[subscript 6]X[subscript 4]=N-C[subscript 6]H[subscript 4]-C[xi]C-H and H-C[xi]C-C[subscript 6]H[subscript 4]-NH-C[subscript 6]X[subscript 4]-NH-C[subscript 6]H[subscript 4]-C[xi]C-H (X=H, F, Cl). These new ligands were reacted with the trans ?PtCl[subscript 2]L[subscript 2] (L=PBu[subscript 3]) complex to form the target polymers. Evidence for conjugation was provided by UV-vis spectroscopy and was corroborated by DFT computations. The ligands, model compounds and polymers sometimes exhibit electrochemically reversible and sometimes irreversible reduction waves (for the quinone diimines) and reversible oxidation waves (for the benzene diamines). These can be either two waves of one electron each, or a single wave involving a two electron transfer process. The new polymers exhibit 10 to 30 units in solution as determined by gel permeation chromatography (GPC). Moreover, these polymers exhibit luminescence properties. The products were characterized by [superscript 1]H and [superscript 31]P NMR, IR, UV-vis, elemental analysis, X-ray crystallography (when possible), TGA (thermogravimetric analysis), electrochemical studies, luminescence spectroscopy, photophysics, and mass spectrometry. The absence of electrical conductivity in the solid state prompted us to investigate the development of dye sensitized solar cells (DSSC) of the Gratzel cell type, since this type does not require the polymer or dye material to be conductive as the regeneration process is accomplished via iodine/iodide in aqueous solution. These DSSC are liquid solar cell as opposed to the solid state plastic cells. The polymers were found to have potential applications in such devices but further analysis is needed for fine tuning and optimisation. The second section of this project (Chapter 3) deals with the anthraquinone diimine and anthracene diamine derivatives. The aim of this structure modification was to increase the rigidity and the stability of the ligand (with respect to those described in Chapter 2) along extending the conjugation and in order to explore a new class of polymers. The anthracenyl residue also includes the possibility of branching redox active pendant groups. Indeed, the antraquinone diimine was studied with different substituents. Bromide and amino groups were used in order to change the electron density in the anthraquinone unit which induce a perturbation on the photophysical properties. These substituents also have an effect on the electrochemical properties. The newly synthesized polymers varied from 5 to 17 units in length, measured using GPC. Moreover, these polymers exhibit luminescence properties. The products were characterized by [superscript 1]H and [superscript 31]P NMR, IR, UV-vis, elemental analysis, X-ray crystallography (when possible), TGA (thermogravimetric analysis), electrochemical studies, luminescence spectroscopy, photophysics, and mass spectrometry. The last sections (Chapter 4 and 5) report the synthesis and characterization ([superscript 1]H and [superscript 31]P NMR, IR, UV-vis and mass spectrometry) of several quinone and anthraquinone dendrimeric ligands and quinone-containing spacers as precursors for future investigations. Due to the embryonic stages of these projects, only structural analysis of the product will be discussed.
- Sciences – Mémoires