Conversion of Metal Pyrazolate/(Hydr)oxide Clusters into Nanojars: Solution vs Solid-State Structure and Magnetism.

Nanojars are a class of anion binding and extraction agents composed of a series of [Cu(µ-OH)(µ-pz)]n (pz = pyrazolate; n = 26-36) supramolecular metal-organic complexes. In contrast to other anion binding agents amenable to liquid-liquid extraction, nanojars only form by self-assembly around the target anion, and guest-free nanojar hosts cannot be isolated. An extraordinary binding strength toward highly hydrophilic anions such as carbonate and sulfate was demonstrated by the inability of Ba2+ ions to precipitate the corresponding insoluble barium salts from nanojars. Herein, we provide an additional proof for the superior robustness of the nanojar framework based on competition experiments with other transition metal pyrazolate/(hydr)oxide complexes. In addition to the mass spectrometric characterization, we present variable-temperature nuclear magnetic resonance studies with an emphasis on the influence of the paramagnetic Cu2+ centers on 1H hyperfine shifts, along with X-ray crystallographic analysis of two polymorphs of (MePh3P)2[CO3⊂{Cu(OH)(pz)}27], including the highest (cubic) symmetry nanojar crystal lattice obtained to date as well as magnetism studies for the first time. Furthermore, we provide evidence for the first molybdate-incarcerating nanojars, [MoO4⊂{Cu(µ-OH)(µ-pz)}n]2- (n = 28, 31-33), formed by rearrangement from [MoVI8O12(µ-O)9(µ-pz)6(pzH)6·3pzH] in the presence of Cu2+ ions.

Chromate Incarceration by Nanojars and Its Removal from Water by Liquid-Liquid Extraction.

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.

An octa-nuclear nickel(II) pyrazolate cluster with a cubic Ni8 core and its methyl- and n-octyl-functionalized derivatives.

The mol-ecular and crystal structure of a discrete [Ni8(µ4-OH)6(µ-4-Rpz)12]2- (R = H; pz = pyrazolate anion, C3H3N2 -) cluster with an unprecedented, perfectly cubic arrangement of its eight Ni centers is reported, along with its lower-symmetry alkyl-functionalized (R = methyl and n-oct-yl) derivatives. Crystals of the latter two were obtained with two identical counter-ions (Bu4N+), whereas the crystal of the complex with the parent pyrazole ligand has one Me4N+ and one Bu4N+ counter-ion. The methyl derivative incorporates 1,2-di-chloro-ethane solvent mol-ecules in its crystal structure, whereas the other two are solvent-free. The compounds are tetra-butyl-aza-nium tetra-methyl-aza-nium hexa-µ4-hydroxido-dodeca-µ2-pyrazolato-hexa-hedro-octa-nickel, (C16H36N)(C4H12N)[Ni8(C3H3N2)12(OH)6] or (Bu4N)(Me4N)[Ni8(µ4-OH)6(µ-pz)12] (1), bis-(tetra-butyl-aza-nium) hexa-µ4-hydroxido-dodeca-µ2-(4-methyl-pyrazolato)-hexa-hedro-octa-nickel 1,2-di-chloro-ethane 7.196-solvate, (C16H36N)2[Ni8(C4H5N2)12(OH)6]·7.196C2H4Cl2 or (Bu4N)2[Ni8(µ4-OH)6(µ-4-Mepz)12]·7.196(ClCH2CH2Cl) (2), and bis-(tetra-butyl-aza-nium) hexa-µ4-hydroxido-dodeca-µ2-(4-octylpyrazolato)-hexa-hedro-octa-nickel, (C16H36N)2[Ni8(C11H19N2)12(OH)6] or (Bu4N)2[Ni8(µ4-OH)6(µ-4-nOctpz)12] (3). All counter-ions are disordered (with the exception of one Bu4N+ in 3). Some of the octyl chains of 3 (the crystal is twinned by non-merohedry) are also disordered. Various structural features are discussed and contrasted with those of other known [Ni8(µ4-OH)6(µ-4-Rpz)12]2- complexes, including extended three-dimensional metal-organic frameworks. In all three structures, the Ni8 units are lined up in columns.

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.

Selective binding of anions by rigidified nanojars: sulfate vs. carbonate.

Selective binding and transport of highly hydrophilic anions is ubiquitous in nature, as anion binding proteins can differentiate between similar anions with over a million-fold efficiency. While comparable selectivity has occasionally been achieved for certain anions using small, artificial receptors, the selective binding of certain anions, such as sulfate in the presence of carbonate, remains a very challenging task. Nanojars of the formula [anion⊂{Cu(OH)(pz)}n]2- (pz = pyrazolate; n = 27-33) are totally selective for either CO32- or SO42- over anions such as NO3-, ClO4-, BF4-, Cl-, Br- and I-, but cannot differentiate between the two. We hypothesized that rigidification of the nanojar outer shell by tethering pairs of pyrazole moieties together will restrict the possible orientations of the OH hydrogen-bond donor groups in the anion-binding cavity of nanojars, similarly to anion-binding proteins, and will lead to selectivity. Indeed, by using either homoleptic or heteroleptic nanojars of the general formula [anion⊂Cun(OH)n(L2-L6)y(pz)n-2y]2- (n = 26-31) based on a series of homologous ligands HpzCH2(CH2)xCH2pzH (x = 0-4; H2L2-H2L6), selectivity for carbonate (with L2 and with L4-L6/pz mixtures) or for sulfate (with L3) has been achieved. The synthesis of new ligands H2L3, H2L4 and H2L5, X-ray crystal structures of H2L4 and the tetrahydropyranyl-protected derivatives (THP)2L4 and (THP)2L5, synthesis and characterization by electrospray-ionization mass spectrometry (ESI-MS) of carbonate- and sulfate-nanojars derived from ligands H2L2-H2L6, as well as detailed selectivity studies for CO32-vs. SO42- using these novel nanojars are presented.

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO2 Sequestration by Selective Binding of Carbonate.

Nanojars are a class of supramolecular anion-incarcerating coordination complexes that self-assemble from Cu2+ ions, pyrazole, and a strong base in the presence of highly hydrophilic anions. In this work, we show that if the strong base (e.g., NaOH or Bu4NOH) is replaced by a weak base such as a trialkylamine, capped nanojars of the formula [{Cu3(µ3-OH)(µ-pz)3L3}CO3⊂{Cu(µ-OH)(µ-pz)}n] (pz = pyrazolate anion; L = neutral donor molecule; n = 27-31) are obtained instead of the conventional nanojars. Yet, to obtain capped nanojars, the conjugate acid side product originating from the weak base must be separated by transferring it to water either by precipitation of the water-insoluble capped nanojars or by liquid-liquid extraction. Full characterization using electrospray ionization mass spectrometry, UV-vis and variable-temperature 1H NMR spectroscopy in solution, and single-crystal X-ray diffraction, elemental analysis, and solubility studies in the solid state reveals similarities as well as drastic differences between capped nanojars and nanojars lacking the [Cu3(µ3-OH)(µ-pz)3L3]2+ cap. Acid-base reactivity studies demonstrate that capped nanojars are intermediates in the pH-controlled assembly-disassembly of nanojars. During the self-assembly of capped nanojars, CO2 is selectively sequestered from air in the presence of other atmospheric gases and converted to carbonate, the binding of which is selective in the presence of NO3-, ClO4-, BF4-, Cl-, and Br- ions.

Doubling the Carbonate-Binding Capacity of Nanojars by the Formation of Expanded Nanojars.

Anion binding and extraction from solutions is currently a dynamic research topic in the field of supramolecular chemistry. A particularly challenging task is the extraction of anions with large hydration energies, such as the carbonate ion. Carbonate-binding complexes are also receiving increased interest due to their relevance to atmospheric CO2 fixation. Nanojars are a class of self-assembled, supramolecular coordination complexes that have been shown to bind highly hydrophilic anions and to extract even the most hydrophilic ones, including carbonate, from water into aliphatic solvents. Here we present an expanded nanojar that is able to bind two carbonate ions, thus doubling the previously reported carbonate-binding capacity of nanojars. The new nanojar is characterized by detailed single-crystal X-ray crystallographic studies in the solid state and electrospray ionization mass spectrometric (including tandem MS/MS) studies in solution.

Identification of metabolites produced during the complete biodegradation of 1-butyl-3-methylimidazolium chloride by an enriched activated sludge microbial community.

Ionic liquids (ILs) are highly polar solvents with unique physicochemical properties that make them promising green alternatives to volatile organic solvents. Since ILs can be toxic to organisms, the development of methods to degrade ILs into harmless molecules prior to disposal is critical to enhancing their green properties. In this study, metabolites generated during the biodegradation of 1-butyl-3-methylimidazolium chloride (BMIMCl) by an enriched, activated sludge microbial community were investigated. Biodegradation of BMIM and the metabolic products released into the growth media were examined using 1H-NMR spectroscopy and mass spectrometry. To the best of our knowledge, this is the first reported complete primary catabolism of the biodegradation-resistant BMIMCl ionic liquid. The bacterial community responsible for degradation was analyzed using a 16S-rRNA amplicon approach. Although the community was diverse, Bacteroidetes was the predominant phylum. The study provides a greater insight into imidazolium-based IL biodegradability and a means to proactively prevent the ecotoxicity of the BMIM cation and its metabolites, by complete primary biodegradation of the cation and removal of most resulting metabolites, prior to release into aquatic waste streams.