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A hydrazine-functionalized, highly stable Al(III) based metal–organic framework (MOF) with CAU-10 (CAU = Christian-Albrechts-University) framework topology namely CAU-10-N2H3 (1) was specifically designed to detect lethal CN ions in aqueous medium. The MOF was characterized by X-ray powder diffraction, infrared spectroscopy, gas sorption and thermogravimetric analyses. The isophthalate ligand in CAU-10 was functionalized by the hydrazine group to make the acidic –NH protons easily available to the CN ions. Indeed, the activated compound (1′) showed highly selective and sensitive responses to CN ions over other common anions with a detection limit of 0.48 μM. A rapid fluorescence enhancement was observed for 1′ with a large spectral shift (Δλ = 30 nm) in the presence of CN ions in aqueous solution with the development of visible green fluorescence under a UV lamp. Due to the excellent detection performance to CN by 1′ in aqueous medium, the material was further used for CN detection in real water samples. The fluorescence increment with a large blue shift is attributed to the cyanide-induced deprotonation of the –NH group, which was confirmed by 1H NMR titration measurements. The initial photo-induced electron transfer (PET) process is prohibited by this deprotonation, which causes the fluorescence enhancement. Time-resolved fluorescence lifetime measurements suggest that 1′ can also act as a lifetime based CN sensor. Finally, the CN sensing ability of 1′ inside living RAW 264.7 macrophages was demonstrated through live-cell imaging investigations.

Graphical abstract: Fluorogenic naked-eye sensing and live-cell imaging of cyanide by a hydrazine-functionalized CAU-10 metal–organic framework

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