Dicyanovinyl substituted triarylboranes: a rational approach to distinguish fluoride and cyanide ions

Abstract

Two new dicyanovinyl (DCV) functionalized triarylboranes (Mes₂B-π-spacer-DCV, for 1: π-spacer = C₆H₄, for 2: π-spacer = 2,3,5,6-tetramethyl-phenyl) are reported. The molecular structures of 1 and 2 are similar except for the spacer which connects the boryl and DCV units. This small structural perturbation induces drastic changes in the optical properties of 1 and 2. Compound 2 shows weak dual fluorescence emission in nonpolar solvents and a stronger emission in polar solvents. Compound 1 is weakly fluorescent in polar environments but shows an intense single luminescence peak in less polar environments. Compound 1 exhibits a turn-off fluorescence response for both fluoride and cyanide: in contrast, 2 shows a turn on fluorescence response for both anions with different fluorescence signatures. The NMR titration studies reveal that for compound 2, fluoride binds to the boron centre and cyanide binds to the DCV unit. For compound 1, the fluoride ion binds to the boron center, whereas the CN⁻ binds to both the Ar₃B and DCV units.