Supramolecular Incarceration and Extraction of Tetrafluoroberyllate from Water by Nanojars

The previously unexplored noncovalent binding of the highly toxic tetrafluoroberyllate anion (BeF₄^2-) and its extraction from water into organic solvents are presented. Nanojars resemble anion-binding proteins in that they also possess an inner anion binding pocket lined by a multitude of H-bond donors (OH groups), which wrap around the incarcerated anion and completely isolate it from the surrounding medium. The BeF₄-binding propensity of [BeF₄⊂{Cu^II(OH)(pz)}]^2- (pz = pyrazolate; n = 27-32) nanojars of different sizes is investigated using an array of techniques including mass spectrometry, paramagnetic ¹H, ⁹Be, and ¹⁹F NMR spectroscopy, and X-ray crystallography, along with thermal stability studies in solution and chemical stability studies toward acidity and Ba²⁺ ions. The latter is found to be unable to precipitate the insoluble BaBeF₄ from nanojar solutions, indicating a very strong binding of the BeF₄^2- anion by nanojars. ⁹Be and ¹⁹F NMR spectroscopy allows for the unprecedented direct probing of the incarcerated anion in a nanojar and, along with ¹H NMR studies, reveals the fluxional structure of nanojars and their inner anion-binding pockets. Single-crystal X-ray diffraction provides the crystal and molecular structures of (Bu₄N)₂[BeF₄⊂{Cu(OH)(pz)}₃₂], which contains a novel Cu-ring combination (x = 9 + 14 + 9), (Bu₄N)₂[BeF₄⊂{Cu(OH)(pz)}₈₊₁₄₊₉], and (Bu₄N)₂[BeF₄⊂{Cu(OH)(pz)}_6+12+10] and offers detailed structural parameters related to the supramolecular binding of BeF₄^2- in these nanojars. The extraction of BeF₄^2- from water into organic solvents, including the highly hydrophobic solvent n-heptane, demonstrates that nanojars are efficient binding and extracting agents not only for oxoanions but also for fluoroanions.