"Caught in the Act" @ disruption of A-ET-E process in the recognition of F- by a lamellar EuIII-MOF in heterogeneous manner with logic gate construction: From protagonist idea to implementation world

Abstract

Development of cost-effective and reliable fluoride sensor for assessing water quality of natural water samples is of immense importance in developing countries as they can provide an easy platform for safeguarding human health. These sensors should be as simple as possible to be fabricated locally by layman. In this context, Eu^III-based MOFs provide trustable platform with bright luminescence in the visible region due to their absorbance-energy transfer-emission (A-ET-E) process. Herein the designed synthesis of a 2D porous coordination polymer, Eu@CMERI, has been carried out following a solvothermal reaction route. The compound shows selective "turn-off" sensing of fluoride in heterogeneous manner from purely aqueous phase and other biological matrices with a detection limit of 28.4 ppb and it carries enormous importance for drinking water analysis under internal regulations. Prohibition of A-ET-E cycle of the Eu^III-MOF is proposed to be the prime reason for fluorescence quenching upon interaction with F^-. DFT studies also revealed that lowest △E_HOMO-LUMO and highest chemical potential value (μ) of F^- are the driving forces for selectivity of Eu^III-MOF towards the targeted anion. The high stability of the porous frameworks along with its interesting sensing features, including fast response and wide linear detection range etc. instigated us not to restrict the chemistry of Eu^III-MOFs at protagonist idea rather to explore its application to real-world analysis. Based on the fluorescence signal exhibited by the targeted analyte, an integrated AND-OR logic gate has also been fabricated which depicts its applicability in molecular electronics. In view of the modular design principle of our polymeric probe, the proposed strategy could open a new horizon to construct powerful sensing materials for ultrafast detection of other important pollutants in the domain of supramolecular chemistry in coming days.

Keywords: A-ET-E Process; Antenna Effect; Aqueous phase F(−) detection; Competitive charge transfer; DFT analyses; ppb level detection.