We describe in this work several polyionic hybrid mol. compds. combining, by electrostatic interactions, liq. cryst. ammonium cations and tailor made molybdenum hexanuclear dianionic cluster units. All hybrids show nematic liq. cryst. behavior below 100 °C, no matter the nature of the metallic cluster apical and inner ligands. They also retain the shiny deep red photoluminescence properties of their parent cluster in the nematic phase. This nematic phase remains however quite viscous for all compds. and mixing them with com. available nematic LCs seems mandatory to integrate them into electroswitchable devices. This particularity conducted us to insert the best candidate in terms of homogeneity and stability of the clustomesogen/com. LC mixt. into a LC cell and study the behavior toward the application of an elec. stimulus. We show that the application of 30 V AC voltage allows observing a reversible modulation of the photoluminescence signal by about 52%. This work presents the first deep red photoluminescent transition metal cluster contg. device directed towards optoelectronic applications.