A Heteronuclear Bidentate Lewis Acid as a Phosphorescent Fluoride Sensor
journal contributionposted on 13.07.2005, 00:00 by Mohand Melaimi, François P. Gabbaï
Reaction of dimesityl-1,8-naphthalenediylborate (1) with C6F5HgCl results in the formation of a B/Hg heteronuclear bidentate Lewis acid (2), which complexes fluoride to afford [2-μ2-F]-. Structural and photophysical studies carried out in solution and in the solid state indicate that 2 is a highly selective and sensitive phosphorescent fluoride sensor. The proximity of the two Lewis acidic sites enforced by the 1,8-naphthalenediyl backbone promotes fluoride anion chelation and is, therefore, responsible for the high binding constant. The interplay of conjugative and spin−orbit coupling effects mediated by the boron and mercury atoms, respectively, results in the phosphorescent signaling of fluoride binding. Remarkably, fluoride binding occurs in partially aqueous solutions and results in a drastic change of the phosphorescence observed when the solutions are frozen.