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 TbIII ions to render the emitted TbIII encapsulated by L2- for lessening non-radiative transitions. The excellent sensitizing capability of the ligand L2- to TbIII 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.

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