A neutral rhenium-biimidazole complex for the selective recognition of fluoride ions

The neutral rhenium(I)-biimidazole complex [Re(CO)₃(biimH)(1,4-NVP)] (1) was designed and synthesized by a one-pot reaction of Re₂(CO)₁₀, 2,2'-biimidazole (biimH₂) and 4-(1-naphthylvinyl)pyridine (1,4-NVP). The structure of 1 was characterized by various spectroscopic techniques including IR, ¹H NMR, FAB-MS, and elemental analysis and further confirmed by a single-crystal X-ray diffraction analysis. The mononuclear complex 1, a relatively simple structure with an octahedral geometry, is comprised of facial-arranged carbonyl groups, one chelated biimH monoanion, and one 1,4-NVP. Complex 1 shows the lowest energy absorption band at around 357 nm and an emission band at 408 nm in THF. The luminescent characteristics of 1 combined with the hydrogen bonding ability of the partially coordinated monoionic biimidazole ligand permits the complex to selectively recognize fluoride ions (F^-) in the presence of other halides through a dramatic luminescence enhancement. The recognition mechanism of 1 can be convincingly explained in terms of H-bond formation and proton abstraction upon the addition of F^- ions by ¹H and ¹⁹F NMR titration experiments. The electronic properties of 1 were further supported by time dependent density functional theory (TDDFT) computational studies.