Intramolecular Hydrogen Bonding in Substituted Aminoalcohols

Lane, Joseph R.; Schrøder, Sidsel D.; Saunders, Graham C.; Kjaergaard, Henrik G.

doi:10.1021/acs.jpca.6b05898

Cited by 43 publications

(49 citation statements)

References 33 publications

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“…Unequivocally, the bcp is the point where one finds no difference between QTAIM and RDG. elucidated in several recent studies by the Kjaergaard group [67][68][69][70][71], in which it was shown that the experimentally-determined weakly bound and van der Waals interactions in molecular systems can be successfully identified and characterized by RDG-NCI, which may or may not be identified with QTAIM due to its stringent criteria.…”

Section: A Reduced Density Gradient (Rdg) Description Of Non-covalentmentioning

confidence: 99%

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Varadwaj

Marques

Yamashita

2018

Materials Today Chemistry

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Methylammonium lead tribromide (CH 3 NH 3 PbBr 3 ) perovskite as a photovoltaic material has attracted a great deal of recent interest. Factors that are important in their application in optoelectronic devices include their fractional contribution of the composition of the materials as well as their microscopic arrangement that is responsible for the formation of well-defined macroscopic structures. CH 3 NH 3 PbBr 3 assumes different polymorphs (orthorhombic, tetragonal and cubic) depending on the evolution temperature of the bulk material. An understanding of the structure of these compounds will assist in rationalizing how halogen-centered non-covalent interactions play an important role in the rational design of these materials. Density functional theory (DFT) calculations have been performed on polymorphs of CH 3 NH 3 PbBr 3 to demonstrate that the H atoms on C of the methyl group in CH 3 NH 3 + entrapped within a PbBr 6 4-perovskite cage are not electronically innocent, as is often contended. We show here that these H atoms are involved in attractive interactions with the surrounding bromides of corner-sharing PbBr 6 4-octahedra of the CH 3 NH 3 PbBr 3 cage to form Br•••H(-C) hydrogen bonding interactions. This is analogous to the way the H atoms on N of the -NH 3 + group in CH 3 NH 3 + form Br•••H(-N) hydrogen bonding interactions to stabilize the structure of CH 3 NH 3 PbBr 3 . Both these hydrogen bonding interactions are shown to persist regardless of the nature of the three polymorphic forms of CH 3 NH 3 PbBr 3 . These, together with the Br•••C(-N) carbon bonding, the Br•••N(-C) pnictogen bonding, and the Br•••Br lump-hole type intermolecular non-covalent interactions identified for the first time in this study, are shown to be collectively responsible for the eventual emergence of the orthorhombic geometry of the CH 3 NH 3 PbBr 3 system. These conclusions are arrived at from a systematic analysis of the results obtained from combined DFT, Quantum Theory of  Corresponding Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/xxxxxxx Atoms in Molecules (QTAIM), and Reduced Density Gradient Non-Covalent Interaction (RDG-NCI) calculations carried out on the three temperature-dependent polymorphic geometries of CH 3 NH 3 PbBr 3 .

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Section: A Reduced Density Gradient (Rdg) Description Of Non-covalentmentioning

confidence: 99%

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Varadwaj

Marques

Yamashita

2018

Materials Today Chemistry

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“…29 NCI theory is a complementary approach to the more traditional Atoms in Molecules (AIM) topological analysis of electron density, 30 and offers some advantages particularly for weak intramolecular hydrogen bonding interactions. 31,32 To date, NCI theory has largely been used for a qualitative interpretation of hydrogen bond strength although Contreras-Garcia et al…”

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confidence: 99%

“…4 This investigation expands on recent work by some of the authors, who showed that the OH-stretching frequency of substituted amino alcohols that exhibit an intramolecular OH-N hydrogen bond correlates well with the kinetic energy integrated within an NCI isosurface volume. 32 Spectra of the gas phase complexes were obtained by subtracting the individual monomer spectra from the spectrum of the mixture (e.g. MeOH + pyridine).…”

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confidence: 99%

Kinetic Energy Density as a Predictor of Hydrogen-Bonded OH-Stretching Frequencies

et al. 2017

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This work considers the nature of the intermolecular hydrogen bond in a series of 15 different complexes with OH donor groups and N, O, P, or S acceptor atoms. To complement the existing literature, room-temperature gas-phase vibrational spectra of the methanol-pyridine, ethanol-pyridine, and 2,2,2-trifluoroethanol-pyridine complexes were recorded. These complexes were chosen, as they exhibit hydrogen bonds of intermediate strength as compared to previous investigations that involved strong or weak hydrogen bonds. Non Covalent Interactions (NCI) theory was used to calculate various properties of the intermolecular hydrogen bonds, which were compared to the experimental OH-stretching vibrational red shifts. We find that the experimental OH-stretching red shifts correlate strongly with the kinetic energy density integrated within the reduced density gradient volume that describes a hydrogen bond [G(s)]. Given that vibrational red shifts are commonly used as a metric of the strength of a hydrogen bond, this suggests that G(s) could be used as a predictor of hydrogen bonding strength.

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“…14 The major gt conformation of 2 and 3 in aqueous base is also consistent with the predominant gauche conformation of neutral ethanol amine as determined by NMR spectroscopy, 14 and computationally, 15 and as determined by vibrational spectroscopy in the gas phase. 16 …”

Section: Resultsmentioning

confidence: 99%

Stereospecific synthesis of methyl 2-amino-2-deoxy-(6S)-deuterio-α,β-d-glucopyranoside and methyl 2,6-diamino-2,6-dideoxy-(6R)-deuterio-α,β-d-glucopyranoside: Side chain conformations of the 2-amino-2-deoxy and 2,6-diamino-2,6-dideoxyglucopyranosides

Kato

Vasella

Crich

2017

Carbohydrate Research

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The stereospecifically labeled 6-monodeuterio methyl 2,6-diamino-2,6-dideoxy-α- and β-D-glucopyranosides were synthesized with a view to determining their side chain conformations. NMR studies in D2O at pH 5 and pH 11 reveal both anomers to adopt very predominantly the gt conformation consistent with the gauche conformation of 2-aminoethanol and its acetate salt. In contrast, as also revealed with the help of stereospecifically-labelled monodeuterio isotopomers, the methyl 2-amino-2-deoxy-α- and β-D-glucopyranosides are an approximately 1:1 mixture of gg and gt conformers as is found in glucopyranose itself.

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Intramolecular Hydrogen Bonding in Substituted Aminoalcohols

Cited by 43 publications

References 33 publications

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Kinetic Energy Density as a Predictor of Hydrogen-Bonded OH-Stretching Frequencies

Stereospecific synthesis of methyl 2-amino-2-deoxy-(6S)-deuterio-α,β-d-glucopyranoside and methyl 2,6-diamino-2,6-dideoxy-(6R)-deuterio-α,β-d-glucopyranoside: Side chain conformations of the 2-amino-2-deoxy and 2,6-diamino-2,6-dideoxyglucopyranosides

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