The comparison of the emission spectra of all the complexes with the ligand shows that the emission of ligand superimposes that of 1-3 (Figure ) thus confirming that the lower energy emissive excited state in the complexes is ligand-centered ( 1 LC). Additionally, the charge transfer feature observed in the complexes from changing the solvent polarity is assigned to the electron donating strength of the thiophene rings attached to the phenanthroline. The lifetime of the complexes and ligand were measured with 375.6 nm picosecond pulsed laser diode at the emission maxima. As shown (Figure , S34, Table , Tables and), 1-3 decay radiatively following the biexponential decay in all the solvents. The radiative decay of L monitored at 467 nm in DMF shows lifetimes of 0.39(±0.01) and 0.61(±0.05) ns while in complexes 1-3 the lifetimes were observed to be 0.32(±0.06), 0.47(±0.02) ns for 1, 0.38(±0.03), 0.53(±0.06) ns for 2, and 0.36(±0.04), 0.51(±0.04) ns for 3. The reduction in the excited state lifetime when compared with L could be explained due to the complexation. However, when the lifetimes of the complexes are compared in all the solvents, the decay pattern for the complexes change with the solvent polarity and observed to decay fast in ACN (Figure , Table , Tables and). The comparison of emission intensity and photoluminescence quantum yield of 1-3 in THF, ACN and DMF (Figure , Table , Tables ) shows that all the complexes emit weakly in ACN while the intensity of emission remains relatively more for THF and DMF. Such difference in the emission behavior of the complexes and ligand in ACN when compared with other solvents suggests the varied behavior of excited state of these complexes in solvents of different polarity. Comparatively, all complexes are relatively strongly emissive in DMF and such differences in observed quantum yields with change of solvent further also imply the effect of solvent to control the excited state dynamic of the complexes.