The luminescent and mesomorphic properties of a series of metal complexes based on hexacatenar 2,2′:6′,2′′-terpyridines are investigated using experimental methods and density functional theory (DFT). Two types of ligand are examined, namely 5,5′′-di(3,4,5-trialkoxyphenyl)terpyridine with or without a fused cyclopentene ring on each pyridine and their complexes were prepared with the following transition metals: ZnII, CoIII, RhIII, IrIII, EuIII and DyIII. The exact geometry of some of these complexes was determined by single X-ray diffraction. All complexes with long alkyl chains were found to be liquid crystalline, which property was induced on complexation. The liquid-crystalline behaviour of the complexes was studied by polarising optical microscopy and small-angle X-ray diffraction. Some of the transition metal complexes (for example, those with ZnII and IrIII) are luminescent in solution, the solid state and the mesophase; their photophysical properties were studied both experimentally and using DFT methods (M06-2X and B3LYP).