Photoactive coordination compounds based on Cu(I) and Ir(III)

Among photoactive coordination compounds, transition-metal complexes with d6 and d10 electronic configuration are of particular interest for light emitting devices (OLEDs, LECs). As d10 emitters, copper(I) complexes attracted research interest due to the abundance of the metal, its relatively low cost and, at the same time, the remarkable photoluminescence quantum yield. Iridium(III) complexes (d6 configuration), on the other hand, show tunable luminescence across the whole visible region and high stability. The first part of this thesis is devoted to the study of copper(I) heteroleptic complexes with general formula [Cu(NN)(PP)]+, where NN = 1,10-phenanthroline or a related derivative and PP = diphosphine, i.e., a bidentate phosphine ligand. In particular, I focussed on their photophysics, electrochemistry and coordination structure, also with the support of DFT calculations. A library of more than thirty [Cu(NN)(PP)]+ complexes has been investigated, evidencing the effects of such chelators on the electronic and structural properties. The second part of this research activity focusses on the study of [Ir(C-N)2(A-A)]n compounds (where C-N are cyclometalated ligands, A-A an ancillary ligand and n = -1, 0). Two unconventional classes of luminescent Ir(III) complexes have been photophysically and electrochemically characterized, one with negative net charge and the other with an unusual ancillary azaborine ligand. The understanding of the electronic factors that control the photophysical properties and the application of these materials in lighting device are the final aim of this PhD work.