A lanthanide luminescent sensor for the detection of 4-nitrophenol in aqueous media

Abstract

The development of facile luminescent sensors for detecting nitrophenols in aqueous media is of great necessity for the safety of the environment and human health, as they are a class of widespread toxic organic pollutants that cause serious adverse effects upon consumption. Based on a new multidentate asymmetric ligand (H₂L) in which salicylamide and 4-nitryl-salicylaldimine are spaced by 1,2-bis(2-ethoxy)ethyl, a new hydrostable lanthanide intercycle, [Tb₂L₂(NO₃)₂]·CH₃CN (Tb-[2]c), was prepared to act as a new luminescent sensor for 4-NP in water media. Structural analysis indicated that two fully deprotonated L²⁻ ligands in cis-configuration and μ₂-L-κ²O¹:κO²:κO⁴:κN²:κO⁵ coordination mode were interlocked by two Tb^III ions to render the emitted Tb^III encapsulated by L²⁻ for lessening non-radiative transitions. The excellent sensitizing capability of the ligand L²⁻ to Tb^III was ascertained by both experimental methods and theoretical calculations. The sensing exploration indicated that Tb-[2]c exhibited highly sensitive and selective recognition of 4-NP against other nitroaromatics in aqueous media. The recognition mechanism could be attributed to the internal filtration effect (IFE) mechanism when DFT calculations and accumulating experimental evidence were combined.