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Thiophenol (PhSH) is an important sulfhydryl compound in organic synthesis, but it is also a volatile environmental pollutant with high toxicity to organisms. Herein, we reported a novel near-infrared (NIR) probe (1) for turn-on fluorescence detection of PhSH. The probe was prepared by coupling 2,4-dinitrophenyl (DNP) to a dicyanoisophorone-based fluorophore (2). PhSH can specifically perform a nucleophilic aromatic substitution on probe 1 and result in the release of fluorophore 2, thus achieving a turn-on fluorescence response (λem = 693 nm). A dramatic c