Selective fluoride sensing by a novel series of lanthanide-based one-dimensional coordination polymers through intramolecular proton transfer
Abstract
A novel series of one-dimensional coordination polymers (CPs) is achieved via a facile one-pot synthesis strategy employing the nitrate salts of trivalent lanthanides, a pentadentate chelating ligand, and triphenylphosphine oxide at a controlled stoichiometry under ambient conditions. All the CPs are characterized comprehensively using spectroscopic, X-ray crystallographic and magnetometric studies. The CPs are found to be thermally stable up to a significantly high temperature and resistant to water for an indefinite time. They are photoactive and exhibit selective fluoride ion (F-) sensing with excellent efficiency both colorimetrically and fluorimetrically in the solid-state as well as in solution. The presence of F- concomitantly sensitizes the photoluminescence enhancement and visual decolourization of the CPs in solution owing to the ground-state intra-molecular proton transfer. The photophysical response of the CPs to F- in solution was found to be instantaneous (<30 s). The sensitivity of detection is observed to be significantly high over a wide range of F- concentrations, covering the beneficial and detrimental domains of F- concentrations in drinking water. The limit of detection (LoD) under ambient conditions was found to be in the micromolar (mu M) range-the best being 0.22 mu M found using UV-vis spectrometry and 7.5 mu M using fluorimetry. In comparison, the USEPA standard cut-off for the upper limit of F- concentration in drinking water is 211 mu M, and the LoD of measuring F- concentration using the USEPA standard method using a fluoride-selective electrode is 26.3 mu M. The CPs display markedly high selectivity toward F- with negligible-to-no interference from the commonly abundant ions (Cl-, Br-, I-, CH3CO2-, CO32-, SO42-, HPO42-, NH4+, Na+, K+, Mg2+, and Ca2+) in terms of UV-vis spectral change. Moreover, they also exhibit solid-state IR-spectrometric sensitivity towards F- under ambient conditions.
