An extensive single-crystal X-ray crystallographic study of 11 nanojar structures (of which seven are novel) of the formula [anion⊂{cis-CuII(μ-OH)(μ-pz)}n]2– (anion = BeF42–, n = 28, 31, 32, CunBeF4; anion = SO42–, n = 28, 31, CunSO4; pz = pyrazolate, C3H3N2–) has been carried out, providing a detailed description of isomorphism and pseudopolymorphism in nanojars. The results point to a remarkable variety in the shape of the constituent [cis-CuII(μ-OH)(μ-pz)]x (Cux; x = 6, 8, 9, 10, 12 and 14) metallamacrocycles, despite only small differences in the coordination environment of the individual Cu2+ centers. The flexibility of the Cux rings and, ultimately, of the nanojar framework allows for the incarceration of different anions with slightly different dimensions in a nanojar of a given size, resulting in the formation of isomorphous structures in the case of CunBeF4 and CunSO4. Selectivity studies monitored by electrospray-ionization mass spectrometry (ESI-MS) and proton nuclear magnetic resonance spectroscopy (1H NMR) reveal that despite the virtually identical H-bonding pattern around the two anions in nanojars of a given size, SO42– is strongly preferred over BeF42–. The origins of this selectivity are discussed, along with the nature of bonding in the two isosteric anions. Lastly, the crystal structure of (Bu4N)3Be2F7(H2O)3 documents the formation of the Be2F73– ion from BeF42–.
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Supramolecular Incarceration and Extraction of Tetrafluoroberyllate from Water by Nanojars
The previously unexplored noncovalent binding of the highly toxic tetrafluoroberyllate anion (BeF42–) 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⊂{CuII(OH)(pz)}n]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 BeF42– 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 Cux-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 BeF42– in these nanojars. The extraction of BeF42– 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.
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- Award ID(s):
- 1808554
- NSF-PAR ID:
- 10330168
- Date Published:
- Journal Name:
- Inorganic Chemistry
- ISSN:
- 0020-1669
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The unprecedented liquid–liquid extraction of the dinegative chromate ion (CrO42–) from neutral aqueous solutions into aliphatic hydrocarbon solvents using nanojars as extraction agents is demonstrated. Transferring chromate from water into an organic solvent is extremely challenging due to its large hydration energy (ΔGh° = −950 kJ/mol) and strong oxidizing ability. Owing to their highly hydrophilic anion binding pockets lined by a multitude of hydrogen bond donor OH groups, neutral nanojars of the formula [cis-CuII(μ-OH)(μ-4-Rpz)]n (n = 27–33; pz = pyrazolate anion; R = H or n-octyl) strongly bind the CrO42– ion and efficiently transfer it from water into n-heptane or C11 – C13 isoalkanes (when R = n-octyl). The extracted chromate can easily be recovered from the organic layer by stripping with an aqueous acid solution. Electrospray ionization mass spectrometric, UV–vis and paramagnetic 1H NMR spectroscopic, X-ray crystallographic, and thermal stability studies in solution and chemical stability studies toward NH3, methanol, and Ba2+ ions are employed to explore the binding of the CrO42– ion by nanojars. Titration of carbonate nanojars [CO3 ⊂ {Cu(OH)(pz)}n]2– with H2CrO4 leads to anion exchange and the formation of chromate nanojars [CrO4 ⊂ {Cu(OH)(pz)}n]2–. Details of chromate binding by H-bonding based on single-crystal structures of (Bu4N)2[CrO4 ⊂ {Cu(OH)(pz)}28], four pseudopolymorphs of (Bu4N)2[CrO4 ⊂ {Cu(OH)(pz)}31], and also the methoxy-substituted derivative (Bu4N)2[CrO4 ⊂ {Cu31(OH)30(OCH3)(pz)31}] are presented.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.inorgchem.2c01198
