Two series of heterocycle-based mesogens consisting of a long 2,5-diphenyl-1,3,4-oxadiazole/thiadiazole rigid core with three lipophilic and flexible alkyl chains at one end and a polar glycerol group at the opposite end have been synthesized via one pot cyclization reaction. These compounds were investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X-ray scattering, cyclic voltammetry, UV-vis spectroscopy and photoluminescence measurements. Upon elongation of the alkyl chains, a transition from hexagonal columnar phase to Pm (3) over barn-type cubic phase was observed in both series. Oxadiazole series are blue luminescent LCs with binding selectivity to Li+, while thiadiazole series are blue-green luminescent LCs with binding selectivity to Fe3+. (C) 2017 Elsevier B.V. All rights reserved.