High-Performance Water Harvester Framework for Triphasic and Synchronous Detection of Assorted Organotoxins with Site-Memory-Reliant Security Encryption via pH-Triggered Fluoroswitching

Abstract

Atmospheric water harvesting, triphasic detection of water contaminants, and advanced antiforgery measures are among important global agendas, where metal-organic frameworks (MOFs), as an incipient class of multifaceted materials, can affect substantial development of individual properties at the interface of tailor-made fabrication. The chemically robust and microporous MOF, encompassing contrasting pore functionalization, exhibits an S-shaped water adsorption curve at 300 K with a steep pore-filling step near P/P0 = 0.5 and shows reversible uptake-release performance. Density functional theory (DFT) studies provide atomistic-level snapshots of sequential insertion of H2O molecules inside the porous channels and also portray H-bonding interactions with polar functional sites in the two-fold interpenetrated structure. The highly emissive attribute with an electron-pull system benefits the fast-responsive framework and highly regenerable detection of four classes of organic pollutants (2,4,6-trinitrophenol (TNP), dichloran, aniline, and nicotine) in water at a record-low sensitivity. In addition to solid-, liquid-, and vapor-phase sensing, host-guest-mediated reversible fluoroswitching is validated through repetitive paper-strip monitoring and image-based detection of food sample contamination. Structure-property synergism in the electron transfer route of sensing is justified from DFT calculations that describe the reshuffling of molecular orbital energy levels in an electron-rich network by each organotoxin, besides evidencing framework-analyte supramolecular interactions. The MOF further delineates the pH-responsive luminescence defect repair via site-specific emission modulation, wherein reversibly alternated "encrypted and decrypted"states are utilized as highly reusable anticounterfeiting labels over multiple platforms and conceptualized as artificial molecular switches. Aiming at self-calibrated, advanced security claims, a NOR-OR coupled logic gate is devised based on commensurate fluorescence-cum-real-time synchronous detection of organic and inorganic (HCl and NH3) pollutants. ©