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.

Integration of robotic inverse kinematic routines in an algorithmic 3D modeling software

An industrial manipulator equipped with an automatic clay extruder is used to realize a machine that can manufacture additively clay objects. The desired geometries are designed by means of a 3D modeling software and then sliced in a sequence of layers with the same thickness of the extruded clay section. The profiles of each layer are transformed in trajectories for the extruder and therefore for the end-effector of the manipulator. The goal of this thesis is to improve the algorithm for the inverse kinematic resolution and the integration of the routine within the development software that controls the machine (Rhino/Grasshopper). The kinematic model is described by homogeneous transformations, adopting the Denavit-Hartenberg standard convention. The function is implemented in C# and it has been preliminarily tested in Matlab. The outcome of this work is a substantial reduction of the computation time relative to the execution of the algorithm, which is halved.