Abstract:
Substituent effect for a series of 5-phenyl tris(8-hydroxyquinolinato) M(III) complexes (Mq3) of aluminum, gallium, and indium are investigated using density functional theory (DFT) for the ground state properties and the time-dependent version of DFT (TDDFT) for their absorption and emission properties. A comparison between the ground state energy of mer and fac isomers of all the complexes revealed that the mer configuration is always more stable than fac. The substituent effect is significantly reflected at the fluorescence maximum (λF ) values whereas the effect is moderate at the absorption maximum (λabs ) values. The molecular electrostatic potential (MESP) at the metal center (VM ) and the most electron rich region indicated by MESP minimum (Vmin ), located at the oxygen of phenoxide ring exhibit excellent correlations with the λF and Stokes shift (λF -λabs ) values. The study suggests the use of Stokes shift as an experimental quantity to measure the excited state substituent effect while the Vmin or VM emerge as theoretical quantities to measure the same.
