ABSTRACT
Polyoxometalate (POM)-based ionic liquids, with nearly infinite compositional variations to fine-tune antimicrobial and physical properties, function as water purification filters, anticorrosion/antibacterial coatings for natural stones, self-repairing acid-resistant coatings, catalysts, and electroactive, stable solvents. By combining hydrophobic quaternary ammonium cations (QACs; tetraheptylammonium and trihexyltetradecylammonium) with butyltin-substituted polyoxotungstates [(BuSn)3(α-SiW9O37)] via repeated solvent extraction-ion exchange, we obtained phase-pure hybrid POM salts (referred to as such because they melt above room temperature). If the solvent extraction process is performed only once, then solids with high salt contamination and considerably lower melting temperatures are obtained. Solution-phase behavior, based on POM-QAC interactions, was similar for all formulations in polar and nonpolar organic solvents, as observed by X-ray scattering and multinuclear magnetic resonance spectroscopy. However, solid thin films of the butyltin-functionalized hybrid POM salts were significantly more stable and adhesive than their inorganic analogues. We attribute this to the favorable hydrophobic interactions between the butyltin groups and the QACs. All synthesized hybrid POM salts display a potent antimicrobial activity toward Escherichia coli. These studies provide fundamental form-function understanding of hybrid POM salts, based on interactions between ions in these complex hybrid phases.
ABSTRACT
We report a hierarchical self-assembly engineering of tin-oxo clusters from nanosized hydrophobic clusters to a single-layer film of assembled clusters. These clusters are derivatives of the previously reported Na-centered butyltin Keggin ions, but they are bicapped with butyltin and with borate ligands. The formulas γ-[( n-BuSn)14(OCH3)10(OH)3O9(NaO4)(HBO3)2] and γ-[( n-BuSn)14(OCH3)10(OH)3O9(NaO4)(PhBO2)2] were determined from single-crystal X-ray diffraction and bulk solution characterization including small-angle X-ray scattering, electrospray ionization mass spectrometry, and multinuclear and multidimensional NMR (119Sn, 13C, and 1H). Solution characterization confirms that borate functionalization inhibits the solution-phase ß-γ Keggin isomer interconversion that was recognized prior for uncapped butyltin clusters, and in this case, the γ isomer is favored. The assembly of the γ-NaSn14BO3 clusters into a homogeneous Langmuir-Blodgett monolayer is the first step toward creating nanopatterned films for microelectronic devices.
