Colorimetric Fluoride Ion Sensing by Boron-Containing π-Electron Systems

The boron-containing pi-conjugated systems, including tri(9-anthryl)borane (1) and tris(10-dimesitylboryl)-9-anthrylborane (2), have been investigated as a new type of fluoride chemosensor. Upon complexation of 1 with a fluoride ion, a significant color change from orange to colorless was observed and, in the UV-visible absorption spectra, the characteristic band of 1 at 470 nm disappeared and new bands around 360-400 nm assignable to pi-pi transitions of the anthryl moieties were observed. This change can be rationalized as a result of the interruption of the pi-conjugation extended through the vacant p-orbital of the boron atom by the formation of the corresponding fluoroborate. The binding constant of compound 1 with the fluoride ion was quite high (2.8 +/- 0.3) x 10(5) M(-1), whereas 1 only showed small binding constants with AcO- and OH- of around 10(3) M(-1) and no sensitivity to other halide ions such as Cl-, Br-, and I-, thus demonstrating its selective sensing ability to the fluoride ion. In contrast to the monoboron system 1, compound 2 having four boron atoms showed multistage changes in the absorption spectra by the stepwise complexation with fluoride ions.