PREPARATION, LUMINESCENCE AND INTERACTIONS WITH LI+, NA+ AND UO22+ OF2 NEW METALLOCALIX[4]ARENE COMPLEXES OF IRIDIUM(I)

Two new complexes of Ir(I) using diphosphine and diphosphinite calix[4 ]arene ligands have been prepared and characterized. The luminescent l owest energy excited MLCT state (metal-to-ligand charge transfer) has been addressed theoretically by extended Huckel molecular orbital calc ulations (EHMO), and a Franck-Condon analysis on the absorption spectr a using the time dependent Heller's theory, has been made. The perturb ation of tau(e) of the two complexes in ethanol at 77 K by the additio n of substrates (UO22+, Li+, Na+), is investigated. The amplitude in t au(e) change with additions of substrates varies as UO22+ > Li+ > Na+.