Novel versatile imine—enamine chemosensor based on 6-nitro-4-oxo-4H-chromene for ion detection in solution, solid and gas-phase: synthesis, emission, computational and MALDI-TOF-MS studies

A new versatile emissive molecular probe (3) derived from 1,5-bis(2-aminophenoxy)-3-oxopenthane bearing two units of 6-nitro-4-oxo-4H-chromene- has been prepared by a Schiff-base condensation method using conventional and green, ultrasound-aided, methods. The dry yellow powder was characterized as the imine species (3). These imine species, however, where found to rapidly convert to their enamine form (4) in solution, under the presence of water traces. This reaction was computationally studied through Density Functional Theory (DFT) in order to investigate the relative stability of the molecular pair 3/4. The sensing properties of the enamine (4) towards various metal ions were investigated via absorption and fluorometric titrations in solution in dichloromethane, acetonitrile and DMSO. The compound shows a fluorescent turn-off response in the presence of Cu2+, Zn2+, Cd2+, Hg2+ and Ag+ over the other metal ions studied, such as Li+, Na+, K+, Ca2+, Co2+ and Ni2+, being stronger for Cu2+ and Hg2+. The gas phase chemosensing abilities of (3) were also explored suggesting (3) as new active MALDI-TOF-MS matrix by two dry methods showing a strong selectivity towards Cu2+ and Ag+. Our preliminary results show promising uses of (3) supported in PPMA films as metal ion solid chemosensor.