The effect of polar substituents on the heterocyclic benzoxazoles

The synthesis, characterization, and mesomorphic properties of a new type of heterocyclic compounds 1, 2 derived from benzoxazole are reported. In order to understand the relationship between the structure and the mesomorphic behavior, compounds containing a variety of polar substituents (i.e., X=H, F, Cl, Br, CH3, CF3, OCH3, NO2, CN, OH, NMe2, COOCH3) on the terminal end were prepared. The phase behavior of these mesogenic compounds was characterized and studied by differential scanning calorimetry (DSC) and polarization optical microscopy. The formation of mesophases was strongly dependent on the electronic and/or the steric factors of the substituents. In general, a mesophase was better induced by introduction of a polar substituent. Compounds (X=H) formed a crystalline phase, however, other compounds, except for X=OH, exhibited nematic or smectic A phases. Interestingly all compounds with electron-donating substituents (X=CH3, OCH3, NMe2) exhibited nematic phases, however, other compounds with electron-withdrawing substituents (X=F, Cl, Br, CF3, NO2, CN, COOCH3) formed smectic A phases. Compounds (X=NO2, CN, COOCH3) have higher clearing temperatures than those of other homologues, and the higher T., was attributed to an enhanced conjugative interaction. However, no linear correlation between the clearing temperature or the temperature range of mesophases with Hammett up constants was found. The fluorescent properties of the compounds were examined. All lambda(max) peaks of the absorption and photoluminescence spectra of compounds occurred at ca. 348-381 and 389-478 nm, respectively. Whereas, the quantum yields of some compounds were relatively low. (c) 2006 Elsevier Ltd. All rights reserved.