An effective design strategy with an efficient synthetic route to xanthene-based far-red to near-infrared dyes is reported. The dyes were prepared by the Suzuki cross-coupling of the electron-poor fluorescein ditriflate with the electron-rich boronic acid/ester-functionalized pyrrole (2C/3C) and indole (2D/3D) moieties. Upon treatment with trifluoroacetic acid, the closed nonfluorescent forms of the dyes (2C and 2D) ring-opened to their fluorescent forms (3C and 3D). The absorption maxima were 665 and 704 nm, while the emission maxima were 717 and 719 nm for 3C and 3D, respectively. The closed forms of the dyes were soluble in chloroform and acetonitrile. To test the efficacy of the dyes as probes, a turn-off fluoride ion probe was prepared from 3C, which consisted of a silyl ester receptor. The probe responded strongly to low concentrations of fluoride, carbonate, and acetate ions, weakly to phosphate ions, but not to the other halogens. Moreover, the probe can detect the minimum concentration of F- in water.