Diseño de sistemas pentafluorofenil-ciclometalados de PtII y PtIV. Estudio de sus propiedades stars

Abstract

This Thesis is focused on the synthesis, characterization, photophysical and computational studies of new Pt(II) and Pt(IV) compounds, containing cyclometalated and pentafluorophenyl groups. This work is divided in four chapters and an experimental part. In the first Chapter, it is described the synthesis of mononuclear non-emissive Pt(IV) derivatives [Pt(bzq)(C6F5)X2(L)] (X = Cl, I, Br; L = dmso, tht), containging one cycloclometalated bzq ligand. Due to our interest in luminescent Pt(IV) systems, the second Chapter is focused on the syntesis of appropiate pentafluorophenyl Pt(II) precursors, [Pt(C^N)(HC^N)(C6F5)] to obtain luminescent homoleptic Pt(IV) derivatives [Pt(C^N)2(C6F5)Cl], through oxidation reactions with PhICl2. The structural and emissive effects of Cl-/(CN-, Mepy, bpe) exhanges are evaluated in the complex with C^N = pbt. All the complexes are fully characterized (RMN and X-ray diffraction studies) and their optical properties are deeply studied with the aid of theoretical calculations. Besides, the cytotoxicity and cellular localization of some of the Pt(II) complexes in dmso are evaluated. The Chapter 3 describes the synthesis and characterization of heteroleptic Pt(IV) complexes [Pt(bzq)(C^N)(C6F5)Cl] with two different cyclometalated ligands, obtained through oxidation reactions of the Pt(II) precursors [Pt(bzq)(HC^N)(C6F5)], which display more efficient emission that the homoleptic Pt(IV) derivatives. The influence of the second C^N ligand on the optical properties (with the aid of DFT and TD-DFT theoretical calculations) of the Pt(IV) complexes are detailled in this Chapter. The last Chapter is focused on the synthesis and study of properties of luminescent monometallic Pt(II) [Pt(bzq)(C6F5)(κ1-dppm)] and bimetallic Pt(II)-Au(I) [Pt(bzq)(C6F5)(μ-dppm)AuCl] derivatives. Besides, the cytotoxicity of both complexes and the cellular localization of the bimetallic derivative are evaluated. Finally, a short description of the synthesis of bimetallic Ti-Au complexes carried out during the stay at Brooklyn College-The City University of New York is shown.