A novel series of liquid crystalline compounds containing 2,4-thiazolidinedione units with varying terminal alkyl chain lengths was successfully synthesized and characterized. The chemical structures of the synthesized compounds were confirmed by FT-IR, ¹H-NMR, and mass spectrometry. The mesomorphic behavior was investigated using polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Compounds [V]₄, [V]₅, and [V]₆ exhibited enantiotropic nematic phases, while compound [V]₈ displayed a smectic A (SmA) phase. No liquid crystalline behavior was observed for compound [V]₃. The liquid crystalline properties were found to depend on the terminal-to-lateral chain length ratio, molecular geometry, and the nature of the linking groups. Additionally, an odd–even effect was observed in the crystal–nematic and nematic–isotropic transition temperatures for certain members of the series. The results highlight the crucial role of terminal chain length and cyano substitution in stabilizing mesophases and tuning the thermal behavior of these 2,4-thiazolidinedione-based liquid cry
