The sysnthesis and characterization of two series of chiral mononuclear palladium(II) azocompounds, (LN(n))Pd(acac)], prepared by bridge splitting reactions or the dinuclear parents {Pd[LN(n)]μ-Cl)}2with thallium acetylacetonate are reported. All the complexes, bearing a stereogenic centre in the alkoxy lateral chain (R*O=R-(−)-2-octyl;S-(−)-β-citronellyl), are mesomorphic. Their thermotropic behaviour has been investigated by differential scanning calorimetry, optical microscopy and X-ray diffraction. Worthy of note, the clearing temperatures of all the compounds are below 70°C. The relationship between ligands, μ-Cl dimers and mononuclear acetylacetonate complexes is discussed.