The water/ZnCl(2) phase diagram in the vicinity of the 75 mol % water composition is reported, demonstrating the existence of a congruently melting phase. Single crystals of this 3-equiv hydrate were grown, and the crystal structure of [Zn(OH(2))(6)][ZnCl(4)] was determined. Synchrotron X-ray and neutron diffraction and IR and Raman spectroscopy along with reverse Monte Carlo modeling demonstrate that a CsCl-type packing of the molecular ions persists into the liquid state. Consistent with the crystalline and liquid structural data, IR spectroscopy demonstrates that the O-H bonds of coordinated water do not exhibit strong intermolecular hydrogen ion bonding but are significantly weakened because of the water's coordination to Lewis acidic zinc ions. The O-H bond weakening makes this system a very strong hydrogen-bond donor, whereas the ionic packing along with the nonpolar geometry of the molecular ions makes this system a novel nonpolar, hydrogen-bonding, ionic liquid solvent.

Sample preparation techniques for carbohydrate analysis using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) are explored, with particular emphasis on analyte/matrix co-crystallization procedures. While carbohydrates are known to prefer 2,5-dihydroxybenzoic acid (2,5-DHB) as the matrix of choice, these analytes are quite specific about matrix crystal structure, which in turn is dependent on the rate of drying of analyte/matrix spots on the MALDI target. With N-acetylglucosamine (GlcNAc) and N-acetylneuraminic acid (sialic acid or NeuAc) as test monosaccharides, significant increases in ion abundances are demonstrated with 2,5-DHB/NeuAc spots (>10-fold improvement) and 2,5-DHB/GlcNAc spots ( approximately 5-fold improvement) with active drying. The fine structure of crystals generated in active and passive drying was investigated using powder diffraction. Passively dried samples were shown to consist of an ordered polymorph, crystallizing in the space group P2(1)/a, while the actively dried samples produced a disordered phase crystallizing in the space group Pa. These data provide the wherewithal to engineer a matrix best suited for carbohydrate analyses.

Using a series of time- and temperature-resolved synchrotron diffraction experiments, the relationship between multiple polymorphs of ZnCl2 and its respective hydrates is established. The δ-phase is found to be the pure anhydrous phase, while the α, β, and γ phases result from partial hydration. Diffraction, gravimetric, and calorimetric measurements across the entire ZnCl2·R H2O, 0 > R > ∞ composition range using ultrapure, doubly sublimed ZnCl2 establish the ZnCl2 : H2O phase diagram. The results are consistent with the existence of crystalline hydrates at R = 1.33, 3, and 4.5 and identify a mechanistic pathway for hydration. All water is not removed from hydrated ZnCl2 until the system is heated above its melting point. While hydration/dehydration is reversible in concentrated solutions, dehydration from dilute aqueous solutions can result in loss of HCl, the source of hydroxide impurities commonly found in commercial ZnCl2 preparations. The strong interaction between ZnCl2 and water exerts a significant impact on the solvent water such that the system exhibits a deep eutectic at a composition of about R = 7 (87.5 mol %) and a eutectic temperature below −60 °C.

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Crystalline and Liquid Structure of Zinc Chloride Trihydrate: A Unique IonicLiquid. -The H 2O/ZnCl2 phase diagram is re-investigated in the vicinity of 75 mol% H 2O. A congruently melting phase with 3 H2O molecules per Zn corresponding to [Zn(OH2)6][ZnCl4] is identified and its structure is determined by single crystal XRD (triclinic, space group P1, Z = 2). Synchrotron X-ray and neutron diffraction and IR and Raman spectroscopy along with reverse Monte Carlo modeling demonstrate that a CsCl-type packing of the molecular ions persists in the liquid state. Consistent with the crystalline and liquid structural data, IR spectroscopy demonstrates that the O-H bonds of coordinated H 2O do not exhibit strong intermolecular H bonding but are significantly weakened because of the coordination of H 2O to Lewis acidic Zn ions. The latter results in the system being a very strong H-bond donor and a novel nonpolar H-bonding ionic liquid solvent. -(WILCOX, R. J.; LOSEY, B. P.; FOLMER, J. C. W.; MARTIN*, J. D.; ZELLER, M.; SOMMER, R.; Inorg. Chem. 54 (2015) 3, 1109-1119, http://dx.doi.org/10.1021/ic5024532 ; Dep. Chem., N. C. State Univ., Raleigh, NC 27695, USA; Eng.) -J. Schramke 16-006