Cooperativity and bond breakage in model X−⋯H3P⋯YZ (X = F, Cl; YZ = HF, ClF, LiF, BeH2) complexes

McDowell, Sean A. C.

doi:10.1016/j.cplett.2016.06.007

Cited by 6 publications

(3 citation statements)

References 25 publications

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“…And indeed there has been some study of cooperativity as it pertains to XBs. The overarching conclusion from this work − confirms the thesis that reinforcement of both bonds occurs when the central unit acts simultaneously as both electron donor and acceptor. Of some particular importance, this same concept applies also when the two noncovalent interactions involved are a XB and a HB. − …”

Section: Introductionsupporting

confidence: 74%

Ability of Peripheral H Bonds to Strengthen a Halogen Bond

Scheiner

2022

J. Phys. Chem. A

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Quantum calculations study the manner in which the involvement of a halogen atom as a proton acceptor in one or more H bonds (HBs) affects the strength of the halogen bond (XB) it can form with a nucleophile aligned with the X σ-hole. A variety of Lewis acids wherein X = F, Cl, Br, and I are attached to a tetrel atom C or Ge engaged in a XB with nucleophile NH3. One, two, and three HF molecules were positioned perpendicular to the XB axis so that they could form a HB to the X atom. Each such HB strengthened the XB by an increment of 1 kcal/mol or more that does not attenuate as each new HB is added, potentially increasing the interaction energy manyfold. Additionally, the presence of one or more HBs facilitates the formation of a XB by molecules which are reluctant to engage in such a bond in the absence of these auxiliary interactions. Even the F atom, which avoids such a XB, can be coaxed to participate in a XB of moderate strength by one or more of these external HBs.

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Section: Introductionsupporting

confidence: 74%

Ability of Peripheral H Bonds to Strengthen a Halogen Bond

Scheiner

2022

J. Phys. Chem. A

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“…This sort of enhancement of the electron-accepting ability of a molecule by its interaction with another is an example of cooperativity, − which is often discussed within the context of HBs but is equally valid with respect to XBs. The overarching conclusion from previous studies of general XB cooperativity − confirms the premise that reinforcement of both bonds occurs when the central unit acts simultaneously as both electron donor and acceptor. And in particular, there are several examples demonstrating the cooperativity between a XB and a HB. − …”

Section: Introductionsupporting

confidence: 59%

Enhancement of Halogen Bond Strength by Intramolecular H-Bonds

Scheiner

2023

J. Phys. Chem. A

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Quantum calculations study the potential of an intramolecular H-bond between the halogen atom (X) of a halobenzene and a substituent placed ortho to it, to amplify the ability of X to engage in a halogen bond (XB) with a Lewis base. H-bonding substituents NH2, CH2CH2OH, CH2OH, OH, and COOH were added to halobenzenes (X = Cl, Br, I). The amino group had little effect, but those containing OH increased the CX···N XB energy to a NH3 nucleophile by about 0.5 kcal/mol; the increment associated with COOH is larger, nearly 2 kcal/mol. These energy increments were approximately doubled if two such H-bonding substituents are present. Combining a pair of ortho COOH groups with an electron-withdrawing NO2 group in the para position has a particularly large effect, raising the XB energy by about 4 kcal/mol, which can amount to as much as a 4-fold magnification.

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“…When the bond distance increased above 1.8 Å, it entered the vibration section and possessed high entropy energy. Subsequently, the dissociation energy increased because breakage of the hydrogen bond interaction required a high energy to overcome the bond’s attractive energy …”

Section: Results and Discussionmentioning

confidence: 99%

Two-Dimensional Infrared Correlation Spectroscopy, Conductor-like Screening Model for Real Solvents, and Density Functional Theory Study on the Adsorption Mechanism of Polyvinylpolypyrrolidone for Effective Phenol Removal in an Aqueous Medium

et al. 2021

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The discharge of industrial effluents, such as phenol, into aquatic and soil environments is a global problem due to its serious negative impacts on human health and aquatic ecosystems. In this study, the ability of polyvinylpolypyrrolidone (PVPP) to remove phenol from an aqueous medium was investigated. The results showed that a significant proportion of phenol (up to 74.91%) was removed using PVPP at pH 6.5. Isotherm adsorption experiments of phenol on PVPP indicated that the best-fit adsorption was obtained using Langmuir models. The response peaks of the hydroxyl groups of phenol (OH) and the carboxyl groups (i.e., CO) of PVPP were altered, indicating the formation of a hydrogen bond between the PVPP and phenol during phenol removal, as characterized using 1D and 2D IR spectroscopy. The resulting complexes were successfully characterized based on their thermodynamic properties, Mulliken charge, and electronic transition using the DFT approach. To clarify the types of interactions taking place in the complex systems, quantum theory of atoms in molecules (QTAIM) analysis, reduced density gradient noncovalent interaction (RDG-NCI) approach, and conductor-like screening model for real solvents (COSMO-RS) approach were also successfully calculated. The results showed that the interactions that occurred in the process of removing phenol by PVPP were through hydrogen bonding (based on RDG-NCI and COSMO-RS), which was identified as an intermediate type (∇2ρ(r) > 0 and H < 0, QTAIM). To gain a deeper understanding of how these interactions occurred, further characterization was performed based on adsorption mechanisms using molecular electrostatic potential, global reactivity, and local reactivity descriptors. The results showed that during hydrogen bond formation, PVPP acts as a nucleophile, whereas phenol acts as an electrophile and the O9 atom (i.e., donor electron) reacts with the H22 atom (i.e., acceptor electron).

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Cooperativity and bond breakage in model X−⋯H3P⋯YZ (X = F, Cl; YZ = HF, ClF, LiF, BeH2) complexes

Cited by 6 publications

References 25 publications

Ability of Peripheral H Bonds to Strengthen a Halogen Bond

Ability of Peripheral H Bonds to Strengthen a Halogen Bond

Enhancement of Halogen Bond Strength by Intramolecular H-Bonds

Two-Dimensional Infrared Correlation Spectroscopy, Conductor-like Screening Model for Real Solvents, and Density Functional Theory Study on the Adsorption Mechanism of Polyvinylpolypyrrolidone for Effective Phenol Removal in an Aqueous Medium

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