Complexes between lanthanide nitrates and a pro-mesogenic 18-membered diaza-substituted coronand are luminescent both as powders and liquid crystals (between 87 and 195°C ), and the phase transitions are detected by monitoring luminescence intensity and lifetime.Liquid crystals are the main components of new-generation cost-saving colour displays and a great deal of research effort has been devoted to their development during the last two decades. 1 One disadvantage of these devices is their relatively low brightness, due to the use of polarisers and colour filters, and one way to overcome this shortcoming is the design of luminescent liquid crystals. While it is rather easy to find either photoluminescent sheets acting as filters or, even, organicbased luminescent liquid crystals, these materials display a broad-band, and usually blue, emission which is of little use in this context. On the other hand cathode-ray tubes rely on trichromatic phosphors emitting narrow bands in three basic colours, blue, green and red, and so do energy-saving luminescent lamps and tubes. Most of these phosphors contain rare-earth ions, Eu II (blue), Tb III (green) and Eu III (red). Henceforth the idea of introducing lanthanide ions in mesogenic phases. Metallomesogens are relatively new in the area of liquid crystals and they combine the properties of a liquid crystalline phase with the optical and magnetic properties of the metal ions they incorporate. The first liquid crystalline phase containing Ln III ions was reported by Piechocki. 2 Initially, it was thought that introducing bulky spherical ions in potentially mesogenic compounds could disrupt the required order to produce mesophases, but it turned out that many lanthanide-containing systems are amenable to form liquid crystalline phases, as reported in a recent comprehensive review article. 3 Basically, there are two ways of designing luminescent lanthanide-containing mesophases. The first, historical, one is the introduction of highly luminescent complexes into known liquid crystalline phases and successful attempts with bdiketonates have been reported. [4][5][6][7] The other one is the synthesis of luminescent complexes displaying mesogenic properties. 8,9 Metal-centred luminescent properties, particularly those of Eu III , have been taken advantage of to probe, at very low temperature, the degree of disorder around the metal ion in metastable liquid crystals based on europium laurate, 8 and to determine the second-rank crystal-field parameter through analysis of the 5 D 0 ? 7 F 1 transition in order to assess the magnetic anisotropy of europium-containing metallomesogens. 10,11 Here we present a new mesogenic class of luminescent lanthanide complexes built from a substituted diaza-18-crown-6 macrocyclic ligand, and we show, for the first time, how luminescence intensity and lifetime can be used to monitor the transitions from crystalline to liquid crystalline phases and vice-versa.Synthetic macrocycles are selective and versatile ligands for the complexation of trivalent ...