Inverse and regular phenyl-azole ligands for luminescent Iridium(III) complexes

In the modern society, light is mostly powered by electricity which lead to a significant increase of the global energy consumption. In order to reduce it, different kinds of electric lamps have been developed over the years; it is now accepted that phosphorescence-based OLEDs offer many advantages over existing light technologies. Iridium complexes are considered excellent candidates for bright materials by virtue of the possibility to easily tune the wavelength of the emitted radiation, by appropriate modifications of the nature of the ligands. It is important to note that the synthesis of Ir(III) blue-emitting complexes is a very challenging goal, because of wide HOMO-LUMO gaps needed for produce a deep blue emission. During my thesis I planned the synthesis of two different series of new Ir(III) heteroleptic complexes, the C and the N series, using cyclometalating ligands containing an increasing number of nitrogens in inverse and regular position. I successfully performed in the synthesis of the required four ligands, i.e. 1-methyl-4-phenyl-1H-imidazole (2), 4-phenyl-1-methyl-1,2,3-triazole (3), 1-phenyl-1H-1,2,3-triazole (6) and 1-phenyl-1H-tetrazole (7), that differ in the number of nitrogens present in the heterocyclic ring and in the position of the phenyl ring. Therefore the cyclometalation of the obtained ligands to get the corresponding Ir(III)-complexes was attempted. I succeeded in the synthesis of two Ir(III)-complexes of the C series, and I carried out various attempts to set up the appropriate reaction conditions to get the remaining desired derivatives. The work is still in progress, and once all the desired complexes will be synthesized and characterized, a correlation between their structure and their emitting properties could be formulated analysing and comparing the photophysical data of the real compounds.

Direct C–H silylation and borylation of biomass derivatives by iridium heterogeneous catalysts

Furfural and its derivatives represent renewable and readily available platforms for a wide range of chemicals. Much attention has been devoted to their functionalization over the last years. TM-catalysed C–H activation has emerged as a powerful tool for synthesizing new C–C and C–X bonds. Moreover, it provides a sustainable way to obtain molecules by reducing waste and saving steps. At the same time, iridium catalysts have proven to be very active in some C–H functionalizations of several (hetero)arenes. Although very promising, this technique is still poorly applied on an industrial scale due to the severe conditions required. Continuous flow chemistry using heterogeneous catalysts appears to be a valuable way to overcome these problems. In this work, we present different solutions for the immobilization of homogeneous iridium complexes on silica gels, using bidentate amines and phosphines as anchoring ligands. We successfully employed the catalysts in C–H silylation and borylation of furfural, using C2 located directing group. In this way, we finally obtained a suitable catalyst that could be potentially applied in continuous-flow chemistry.