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- ItemHydrogen Bonding Between Ions of Like Charge in Ionic Liquids Characterized by NMR Deuteron Quadrupole Coupling Constants—Comparison with Salt Bridges and Molecular Systems(Weinheim : Wiley-VCH, 2019) Khudozhitkov, Alexander E.; Neumann, Jan; Niemann, Thomas; Zaitsau, Dzmitry; Stange, Peter; Paschek, Dietmar; Stepanov, Alexander G.; Kolokolov, Daniil I.; Ludwig, RalfWe present deuteron quadrupole coupling constants (DQCC) for hydroxyl-functionalized ionic liquids (ILs) in the crystalline or glassy states characterizing two types of hydrogen bonding: The regular Coulomb-enhanced hydrogen bonds between cation and anion (c–a), and the unusual hydrogen bonds between cation and cation (c–c), which are present despite repulsive Coulomb forces. We measure these sensitive probes of hydrogen bonding by means of solid-state NMR spectroscopy. The DQCCs of (c–a) ion pairs and (c–c) H-bonds are compared to those of salt bridges in supramolecular complexes and those present in molecular liquids. At low temperatures, the (c–c) species successfully compete with the (c–a) ion pairs and dominate the cluster populations. Equilibrium constants obtained from molecular-dynamics (MD) simulations show van't Hoff behavior with small transition enthalpies between the differently H-bonded species. We show that cationic-cluster formation prevents these ILs from crystallizing. With cooling, the (c–c) hydrogen bonds persist, resulting in supercooling and glass formation. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemCyclic Octamer of Hydroxyl-functionalized Cations with Net Charge Q=+8e Kinetically Stabilized by a ‘Molecular Island’ of Cooperative Hydrogen Bonds(Weinheim : Wiley-VCH Verl., 2020) Philipp, Jule Kristin; Fritsch, Sebastian; Ludwig, RalfCyclic octamers are well-known structural motifs in chemistry, biology and physics. These include covalently bound cyclic octameric sulphur, cylic octa-alkanes, cyclo-octameric peptides as well as hydrogen-bonded ring clusters of alcohols. In this work, we show that even calculated cyclic octamers of hydroxy-functionalized pyridinium cations with a net charge Q=+8e are kinetically stable. Eight positively charged cations are kept together by hydrogen bonding despite the strong Coulomb repulsive forces. Sufficiently long hydroxy-octyl chains prevent “Coulomb explosion” by increasing the distance between the positive charges at the pyridinium rings, reducing the Coulomb repulsion and thus strengthen hydrogen bonds between the OH groups. The eightfold positively charged cyclic octamer shows spectroscopic properties similar to those obtained for hydrogen-bonded neutral cyclic octamers of methanol. Thus, the area of the hydrogen bonded OH ring represents a ‘molecular island’ within an overall cationic environment. Although not observable, the spectroscopic properties and the correlated NBO parameters of the calculated cationic octamer support the detection of smaller cationic clusters in ionic liquids, which we observed despite the competition with ion pairs wherein attractive Coulomb forces enhance hydrogen bonding between cation and anion. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemSpectroscopic Evidence for Clusters of Like-Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding(Weinheim : Wiley-VCH, 2016) Knorr, Anne; Stange, Peter; Fumino, Koichi; Weinhold, Frank; Ludwig, RalfInfrared spectroscopy and density functional theory calculations provide strong evidence for the formation of clusters of like-charged ions in ionic liquids. With decreasing temperature, cooperative hydrogen bonding overcomes repulsive electrostatic interaction. The resulting cyclic tetramers nicely resemble well-known molecular clusters of alcohols.
- ItemPseudohalogen Chemistry in Ionic Liquids with Non-innocent Cations and Anions(Weinheim : Wiley-VCH-Verl., 2020) Arlt, Sören; Bläsing, Kevin; Harloff, Jörg; Laatz, Karoline Charlotte; Michalik, Dirk; Nier, Simon; Schulz, Axel; Stoer, Philip; Stoffers, Alrik; Villinger, AlexanderWithin the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non-innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT-IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ-nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa-substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non-innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemProbing molecular interaction in ionic liquids by low frequency spectroscopy: Coulomb energy, hydrogen bonding and dispersion forces(London [u.a.] : Royal Society of Chemistry, 2014) Fumino, K.; Reimann, S.; Ludwig, R.Ionic liquids are defined as salts composed solely of ions with melting points below 100 °C. These remarkable liquids have unique and fascinating properties and offer new opportunities for science and technology. New combinations of ions provide changing physical properties and thus novel potential applications for this class of liquid materials. To a large extent, the structure and properties of ionic liquids are determined by the intermolecular interaction between anions and cations. In this perspective we show that far infrared and terahertz spectroscopy are suitable methods for studying the cation-anion interaction in these Coulomb fluids. The interpretation of the measured low frequency spectra is supported by density functional theory calculations and molecular dynamics simulations. We present results for selected aprotic and protic ionic liquids and their mixtures with molecular solvents. In particular, we focus on the strength and type of intermolecular interaction and how both parameters are influenced by the character of the ions and their combinations. We show that the total interaction between cations and anions is a result of a subtle balance between Coulomb forces, hydrogen bonds and dispersion forces. For protic ionic liquids we could measure distinct vibrational modes in the low frequency spectra indicating clearly the cation-anion interaction characterized by linear and medium to strong hydrogen bonds. Using isotopic substitution we have been able to dissect frequency shifts related to pure interaction strength between cations and anions and to different reduced masses only. In this context we also show how these different types of interaction may influence the physical properties of ionic liquids such as the melting point, viscosity or enthalpy of vaporization. Furthermore we demonstrate that low frequency spectroscopy can also be used for studying ion speciation. Low vibrational features can be assigned to contact ion pairs and solvent separated ion pairs. In conclusion we showed how detailed knowledge of the low frequency spectra can be used to understand the change in interaction strength and structure by variation of temperature, solvent polarity and solvent concentration in ionic liquids and their mixtures with molecular solvents. In principle the used combination of methods is suitable for studying intermolecular interaction in pure molecular liquids and their solutions including additive materials such as nanoparticles.
- ItemThree in One: The Versatility of Hydrogen Bonding Interaction in Halide Salts with Hydroxy-Functionalized Pyridinium Cations(Weinheim : Wiley-VCH Verl., 2021) Al Sheakh, Loai; Niemann, Thomas; Villinger, Alexander; Stange, Peter; Zaitsau, Dzmitry H.; Strate, Anne; Ludwig, RalfThe paradigm of supramolecular chemistry relies on the delicate balance of noncovalent forces. Here we present a systematic approach for controlling the structural versatility of halide salts by the nature of hydrogen bonding interactions. We synthesized halide salts with hydroxy-functionalized pyridinium cations [HOCn Py]+ (n=2, 3, 4) and chloride, bromide and iodide anions, which are typically used as precursor material for synthesizing ionic liquids by anion metathesis reaction. The X-ray structures of these omnium halides show two types of hydrogen bonding: 'intra-ionic' H-bonds, wherein the anion interacts with the hydroxy group and the positively charged ring at the same cation, and 'inter-ionic' H-bonds, wherein the anion also interacts with the hydroxy group and the ring system but of different cations. We show that hydrogen bonding is controllable by the length of the hydroxyalkyl chain and the interaction strength of the anion. Some molten halide salts exhibit a third type of hydrogen bonding. IR spectra reveal elusive H-bonds between the OH groups of cations, showing interaction between ions of like charge. They are formed despite the repulsive interaction between the like-charged ions and compete with the favored cation-anion H-bonds. All types of H-bonding are analyzed by quantum chemical methods and the natural bond orbital approach, emphasizing the importance of charge transfer in these interactions. For simple omnium salts, we evidenced three distinct types of hydrogen bonds: Three in one!