Selective fluoride sensing by a novel series of lanthanide-based one-dimensional coordination polymers through intramolecular proton transfer

Vaibhav Singh (1) , Lakshmi Thachanadan Suresh (1) , Jean-Pascal Sutter (2) , Arun Kumar Bar (1)

1 IISER Tirupati - Indian Institute of Science Education and Research (IISER) Tirupati
2 LCC - Laboratoire de chimie de coordination

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 (μM) range—the best being 0.22 μM found using UV-vis spectrometry and 7.5 μM using fluorimetry. In comparison, the USEPA standard cut-off for the upper limit of F− concentration in drinking water is 211 μM, and the LoD of measuring F− concentration using the USEPA standard method using a fluoride-selective electrode is 26.3 μM. 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.

Mots clés: Synthetic procedures; UV-Vis; IR

Domaines: Matériaux

Vaibhav Singh, Lakshmi Thachanadan Suresh, Jean-Pascal Sutter, Arun Kumar Bar. Selective fluoride sensing by a novel series of lanthanide-based one-dimensional coordination polymers through intramolecular proton transfer. Dalton Transactions, 2024, 53 (17), pp.7436-7449. ⟨10.1039/d4dt00598h⟩. ⟨hal-04550862⟩