Two different coumarin derivatives have been connected via an imine linkage to obtain a new fluorescence signaling system. This compound itself does not show any emission due to rapid isomerization around the C=N bond. However, in the presence of a Mg(II) ion, this isomerization is stopped because of bonding to the metal ion resulting in high-intensity (∼550-fold) emission. Other metal ions like Li(I), Ca(II), and Zn(II) show very little emission, while biologically relevant transition-metal ions do not show any emission. In this way, the Mg(II) ion can be detected in the presence of these ions. © 2008 American Chemical Society.