A selective, sensitive, colorimetric, and fluorescence probe for relay recognition of fluoride and Cu(II) ions with "off-on-off" switching in ethanol-water solution.

Anion to cation relay recognition was designed and realized for the first time with sequence specificity (F(-)→Cu(2+)) via a fluorescence "off-on-off" mechanism. Probe 1 was a highly selective, sensitive, and turn-on chemodosimeter for F(-) through a specific cyclization reaction triggered by the strong affinity of fluoride toward silicon with a significant change of fluorescence color in both ethanol and ethanol-water (1:1, v/v) solution. Fluorescence enhancement factors were dramatic: 833-fold in ethanol and 164-fold in ethanol-water (1:1, v/v) solution, respectively. The in situ system generated from the sensing of F(-) showed good relay recognition ability for Cu(2+) via fast fluorescence quenching by the formation of a 1:1 complex in ethanol-water (1:1, v/v) solution. The isolated pure compound 2 also exhibited high selectivity toward Cu(2+) in PBS buffer (pH = 7.0) solution. The origin of this sequence specificity of fluorescence recognition was disclosed through the crystal or optimized structures and DFT calculations of corresponding compounds.