摘要： The effect of introducing a lateral methyl substitution into the previously investigated laterally neat four-ring analogues, 4-substituted phenylazo phenyl 4?-(4?-alkoxyphenylazo) benzoates (Ina–e), on their mesophase behaviour was investigated for the newly prepared five homologous series of 4-substituted phenylazo phenyl 4?-(3?-methyl-4?-alkoxyphenylazo) benzoates (IIna–e). Within each homologous series, the alkoxy group varies between 6, 8, 10, 12, 14, and 16 carbons, while the substituent, X, is a polar group that alternatively changes between the electron-donating (CH3O and CH3) groups, and the electron-withdrawing (Br and NO2) groups, including the unsubstituted homologues (IInc). Their mesophase stabilities were determined by DSC and phases identified by PLM. The results showed that independent of the alkoxy-chain length or the polarity of the substituent X, the nematic phase is predominant with relatively high stability and wide temperature ranges. All compounds show a good thermal stability in the mesophases domain, except the nitro and Br substituted derivatives bearing short alkoxy chain length. Comparison of the mesophase behaviour was also made between the present series and corresponding three-ring laterally CH3-substituted azo/ester analogues. UV-vis absorption spectra revealed that derivatives with electron donating or an electron withdrawing groups exhibited redshifts of the π→π* transition compared with unsubstituded derivative.