Novel π–extended dibenzophenazine based discotic mesogens tethered with alkane thiols and alkoxy phenylacetylene along with alkoxy chains have been designed and synthesised. Molecular structures of all compounds were investigated using spectral and elemental analysis. The liquid crystalline properties of all the novel compounds were characterized using polarised optical microscopy (POM) and differential scanning calorimetry (DSC). The self-assembly of mesophase structure of discotic mesogens were examined with the help of X-ray diffraction studies. All compounds exhibit stable hexagonal columnar mesophase over broad temperature range. The photophysical properties of these compounds were studied in anhydrous chloroform solvent at room temperature which exhibit absorption at 446–463 nm and corresponding emission at 578–600 nm. The high delocalization of π–electrons in extended dibenzophenazine discotic mesogens may find potential applications in devices like, solar cells, sensors, organic light emitting diodes, thin film transistors, etc. © 2020 Elsevier B.V.