Colorimetric and ratiometric near-infrared fluorescent cyanide chemodosimeter based on phenazine derivatives

Two new near-infrared chemodosimeters for cyanide anion based on 5,10-dihexyl-5,10-dihydrophenazine were designed and synthesized. With dicyano-vinyl groups as the recognition site and electron-withdrawing groups on both sides, probe 1 exhibited an intramolecular charge transfer (ICT) absorption band at 545 nm and emission band at 730 nm, respectively, and thus showed an ICT block process and realized an "on-off" response after bilateral reaction with cyanide anions in CH₃CN. Probe 2 utilized an unreactive formyl group instead of one of the two reactive dicyano-vinyl groups as the electron-withdrawing component. Due to the unilateral recognition process the ICT of probe 2 was redirected and lead to a remarkably colorimetric and ratiometric near-infrared (NIR) fluorescent response for cyanine. Both probes provided high sensitivity and selectivity with apparent response signals which can be observed by naked eyes, even in the copresence of various other interference anions. Optical spectroscopic techniques, NMR titration measurements, and density functional theory calculations were conducted to rationalize the sensing mechanisms of these two probes.