Stable complexes [Ti(1a)(2)2] and [Ti(1b)(2)2], where 2 is the 6,6'-diphenyl-2,2'-biphenolato ligand and 1a and 1b ligands are 2,2'-bipyrimidine derivatives, are synthesized. The complex [Ti(1b)(2)2] containing a diimine ligand substituted with long alkyl chains (C16) exhibits a liquid crystal behaviour. This property and self-assembling in the crystalline state are explained by the particular molecular conformation of the complexes.