Studies on Halogen Bonding in Solution, the Solid State, and the Calculated Gas Phase: Towards a Hexameric Halogen Bonding-Based Capsule PDF Download

Author: Elric Engelage
Publisher:
ISBN: 9783843943628
Category :
Languages : en
Pages :

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Author: Pierangelo Metrangolo
Publisher: Springer
ISBN: 3319140574
Category : Science
Languages : en
Pages : 286

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The nature and directionality of halogen bonding; the sigma hole, by Timothy Clark, Peter Politzer, Jane S. Murray Solid-state NMR study of halogen-bonded adducts, by David Bryce Infrared and Raman measurements of halogen bonding in cryogenic solutions, by Wouter Herrebout Halogen bonding in the gas phase, by Anthony C. Legon Halogen bonding in solution, Mate Erdelyi Unconventional motifs for halogen bonding, by Kari Rissanen Halogen bonding in supramolecular synthesis, Christer Aakeröy Halogen bond in synthetic organic chemistry, Stefan M. Huber Anion recognition in solution via halogen bonding, Mark S. Taylor Anion transport with halogen bonds, by Stefan Matile Halogen bonding in silico drug design, by Pavel Hobza, Kevin Riley Biological halogen bonds: An old dog with new tricks, by P. Shing Ho Principles and applications of halogen bonding in medicinal chemistry, by Frank M. Boeckler Halogen bond in molecular conductors and magnets, by Marc Foumigué Halogen bonding towards design of organic phosphors, by Wei Jun Jin Halogen bond in photoresponsive materials, by Pierangelo Metrangolo, Giuseppe Resnati, Arri Priimagi

Author:
Publisher: Faraday Discussions
ISBN: 9781782629559
Category : Science
Languages : en
Pages : 512

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The halogen bond may be considered as a special case of sigma-hole bonding, wherein an electron donor interacts with the electrophilic region of a halogen atom. Within this broader picture, sigma-hole bonding can encompass a range of non-covalent interactions which are named after the atom bearing the electrophilic region, also known as the sigma-hole. This Faraday Discussion unites experimentalists and theoreticians, who are pushing the applicability of this broad class of interactions far beyond only the halogens. The book develops a fundamental understanding of key aspects of non-covalent interactions in solid-state materials, solution chemistry, biochemistry and the gas phase.

Author: Stefan Huber
Publisher: John Wiley & Sons
ISBN: 352782572X
Category : Technology & Engineering
Languages : en
Pages : 416

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Long-awaited on the importance of halogen bonding in solution, demonstrating the specific advantages in various fields - from synthesis and catalysis to biochemistry and electrochemistry! Halogen bonding (XB) describes the interaction between an electron donor and the electrophilic region of a halogen atom. Its applicability for molecular recognition processes long remained unappreciated and has mostly been studied in solid state until recently. As most physiological processes and chemical reactions take place in solution, investigations in solutions are of highest relevance for its use in organic synthesis and catalysis, pharmaceutical chemistry and drug design, electrochemistry, as well as material synthesis. Halogen Bonding in Solution gives a concise overview of halogen bond interactions in solution. It discusses the history and electronic origin of halogen bonding and summarizes all relevant examples of its application in organocatalysis. It describes the use of molecular iodine in catalysis and industrial applications, as well as recent developments in anion transport and binding. Hot topic: Halogen bonding is an important interaction between molecules or within a molecule. The field has developed considerably in recent years, with numerous different approaches and applications having been published. Unique: There are several books on halogen bonding in solid state available, but this will be the first one focused on halogen bonding in solution. Multi-disciplinary: Summarizes the history and nature of halogen bonding in solution as well as applications in catalysis, anion recognition, biochemistry, and electrochemistry. Aimed at facilitating exciting future developments in the field, Halogen Bonding in Solution is a valuable source of information for researchers and professionals working in the field of supramolecular chemistry, catalysis, biochemistry, drug design, and electrochemistry.

Author: Mohammed Sarwar
Publisher: LAP Lambert Academic Publishing
ISBN: 9783659167393
Category :
Languages : en
Pages : 204

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Halogen bonding (XB), the interaction between electron deficient halogen atoms and electron donors, is an established non-covalent interaction in the solid and gaseous phases. To overcome the limitations of the understanding of XB, we investigate XB interactions in solution and design anion receptors. At first, a review of XB interaction: theoretical models, studies of XB in solid and gaseous phases and examples in biological systems are discussed. Then linear free energy relationships involving the thermodynamics of XB are studied. The utility of substituent constants and calculated molecular electrostatic potentials of XB donor ability are discussed. DFT calculations are shown to have useful predictive values for trends in halogen bond strength. We also developed XB based new multidentate anion receptors which exhibit significantly higher binding constants than monodentate donors. Using FNMR, the enthalpies and entropies of anion bindings for mono and tridentate receptors were determined and showed a +Ve entropy contribution to anion binding for both receptors in acetone solvent. These findings can allude to utility in organic synthesis, supramolecular chemistry and drug design

Author: Md. Golam Sarwar
Publisher:
ISBN:
Category :
Languages : en
Pages :

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Author: Pierangelo Metrangolo
Publisher: Springer Science & Business Media
ISBN: 3540743294
Category : Science
Languages : en
Pages : 230

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With contributions by numerous experts

Author: Yijue Xu
Publisher:
ISBN:
Category :
Languages : en
Pages :

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The nature and potential application of halogen bonding are currently topics of great interest among various research fields, including biochemistry, functional materials, organocatalysis, etc. Solid-state nuclear magnetic resonance (SSNMR) has been recognized as one of the important tools for characterizing different types of non-covalent interactions. This dissertation demonstrates how different SSNMR methods can be used to characterize the changes in electronic structure associated with halogen bonding interactions and investigates the processes leading to the formation of halogen bonds. A series of cocrystals featuring halogen bonds between phosphine oxides and different diiodoperfluorobenzenes (1,4-diiodotetrafluorobenzene, 1,2-diiodotetrafluorobenzene, and 1,3,5-trifluoro-2,4,6-triiodobenzene) have been synthesized through slow evaporation from solvent or by mechanochemistry. We began by characterizing the naturally abundant and 17O-labeled phosphine oxides and their halogen-bonded cocrystals by a combination of theoretical and experimental multinuclear magnetic resonance spectroscopy (31P and 17O), and X-ray diffraction (XRD) methods. This first study of 17O NMR parameters in halogen-bonded solids has provided key insights into the correlation between NMR observables and the nature of the halogen bond. Then a rare example of a cocrystal featuring a phosphine as a halogen bond acceptor was synthesized and characterized by both solution and solid-state NMR experiments, and the 31P NMR experiment acted as a direct probe for the formation of halogen bonds in both solution and solid states. In addition to the conventional polycrystalline solid-state NMR experiments, single-crystal NMR studies were performed on 17O labeled triphenylphosphine oxide and its halogen-bonded cocrystals with diiodoperfluorobenzenes, which allowed for the measurement of not only the magnitude but also the orientation of the NMR tensors. The work helped investigate the changes in NMR tensor orientation caused by the formation of halogen bonds and thereby provides a novel connection between the electronic structure and the NMR interactions. Novel single-crystal NMR analysis software was developed to fit the data in two ways: either through an unconstrained fitting process or through a constrained fitting process, which can improve the precision of the resulting tensor orientations in some cases. The mechanochemical production of halogen bonds inspired us to investigate the mechanism and kinetics behind this solid-state reaction process in situ. In situ 31P solid-state NMR studies of halogen bond formation between triphenylphosphine oxide and 1,4-diiodotetrafluorobenzene were carried out under different conditions (temperature, spinning speed, and different amounts of liquid added) to provide insight into the crystallization process and provide an estimation of the activation energy. Overall, this thesis provides several new applications of NMR spectroscopy to the study of halogen bonds and provides various novel insights into the connection between the NMR observables and the nature of this non-covalent interaction.

Author: Michael George Chudzinski
Publisher:
ISBN:
Category :
Languages : en
Pages :

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This thesis focuses on the solution-phase measurement and computational modelling of noncovalent interactions; specifically, complexes formed of halogen-bond donor, hydrogen-bond donor and organoboron compounds with various substrates are investigated. Chapter 1 introduces halogen bonding and provides a review of the solution-phase literature, with a focus on the thermodynamics of the interaction and the use of halogen bonding in anion sensing and catalytic applications. Chapter 2 describes correlations between experimental, solution-phase thermodynamic data and calculated, gas-phase energies of interaction for halogen bonding complexes formed of a diverse set of organic and inorganic iodine donors with Lewis bases, with energies of interaction spanning 7 kcal/mol. Of 23 quantum mechanical modelling methods examined, the B97-1, B97-2 and B98 DFT functionals provide excellent correlations: a feat considering the varying nature of the complexes studied. These results are contrasted with those obtained for a set of hydrogen bonding data, for which different DFT methods (M06-2X, M05-2X) provided the best results. Chapter 3 describes the synthesis and binding traits of anion receptors containing halogen- and hydrogen-bond donor moieties. Neutral receptors composed of urea and iodoperfluoroarene groups bind halides selectively over oxo-anions when compared with receptors lacking halogen-bond donors. Charged halogen-bonding receptors loosely based on imidazolium structures and designed for two-point binding were examined. The receptors are very sensitive to basic conditions and their anion binding properties do not differ significantly from control receptors lacking halogen-bond donors. In general, the anion receptor design, particularly linear halogen bonding angles between substrate and receptor, was found to be important for efficient binding as rationalized through computational modelling of the complexes. Chapter 4 examines the binding affinities of diphenylborinic acid with various diol substrates as determined by indicator-displacement assays. The results are contrasted with measurements for a boronic acid with a similar pKa. The two compounds reveal significant differences in terms of the kinetics and thermodynamics of their interactions with diols: in particular, diphenylborinic acid displays an unusually high level of discrimination for catechol over carbohydrates. Attempts to rationalize the selectivity are made by way of computational modelling.

Author: Lee Jordan Salsberg
Publisher:
ISBN: 9780494524749
Category :
Languages : en
Pages : 224

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An investigation into solvent and substituent effects on halogen bonding strength in solution are described. Through initial investigations towards applications in catalysis, we quickly realized that information concerning halogen bonding interactions in solution are quite limited, and quantitative studies examining solvent and substituent effects are even more rare. Herein, an investigation as to the solvent effects on the halogen bond interaction of perfluorooctyliodide and triethylamine is reported. Also, an examination of para-substituent effects on the interaction of iodotetraflurobenzene analogs with triethylamine is discussed. Through 19F NMR binding isotherm experiments which involved varying the concentration of halogen bond acceptor (triethylamine), while keeping that of the donor constant, an association constant was calculated for all systems. Correlating the calculated association constants with various parameters of the system in question was attempted, with the goal of identifying trends and relationships in modeling the data.