The synthesis and characterization of fused-ring thiadiazoloquinoxaline derivatives are described. The target molecules were studied by UV-Vis absorption, emission spectroscopy and cyclic voltammetry. The optical absorption maximum λ_max of the new molecules in solution were shown at 714–774 nm, with the corresponding optical gaps (E^opt_g) of 1.44–1.50 eV. Density functional theory calculations were applied for the design and prediction of HOMO and LUMO variations and the corresponding optical absorptions. The thiadiazoloquinoxaline with a phenanthroline moiety showed a liquid crystalline phase as found from 2D-WAXS studies and an electron transporting behavior indicating its potential as an acceptor building block.