Anticooperativity of FHF hydrogen bonds in clusters of the type F− × (HF)n, RF × (HF)n and XF × (HF)n, R = alkyl and X = H, Br, Cl, F

Kucherov, S. Yu.; Бурейко, С. Ф.; Денисов, Г. С.

doi:10.1016/j.molstruc.2015.10.066

Cited by 19 publications

(16 citation statements)

References 96 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However these distances are observed in the [FHF] − …HF complex. This complex was observed in earlier studies [27][28][29] and is also analyzed here; it possesses C2v symmetry and may be considered as the F3H2 − anion. The (MP2/aug-cc-pVTZ level) F-H and H…F distances calculated here for this complex are equal to 1.008 and 1.343 Å, respectively (Table 1) which is in agreement with the previous MP2/6-31+G** calculations where 1.012 and 1.349 Å distances were found [27].…”

Section: The Geometry Of the [Fhf]´anionsupporting

confidence: 52%

“…(HF) 2 cluster on the other hand. Such a system has been analyzed previously both experimentally and theoretically [27][28][29].…”

Section: Discussionmentioning

confidence: 99%

“…Figure 5 presents also the continuous line passing through the points corresponding to the hydrogen bifluoride anions possessing D 8h and C 2v symmetries; theoretical results are presented (free [FHF]´anion and its complexes with Na + , Li + cations) as well as species found in the crystal structures. [27][28][29] and is also analyzed here; it possesses C 2v symmetry and may be considered as the F 3 H 2´a nion. The (MP2/aug-cc-pVTZ level) F-H and H .…”

Section: The Geometry Of the [Fhf]´anionmentioning

confidence: 99%

“…There have been earlier studies where the symmetric and asymmetric hydrogen bifluoride anions were considered [26][27][28][29][30][31][32][33][34][35][36][37]. However in this study the emphasis is put on electron charge redistribution being the result of complexation.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

[FHF]−—The Strongest Hydrogen Bond under the Influence of External Interactions

Grabowski

2015

Crystals

View full text Add to dashboard Cite

Section: The Geometry Of the [Fhf]´anionsupporting

confidence: 52%

“…(HF) 2 cluster on the other hand. Such a system has been analyzed previously both experimentally and theoretically [27][28][29].…”

Section: Discussionmentioning

confidence: 99%

Section: The Geometry Of the [Fhf]´anionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

[FHF]−—The Strongest Hydrogen Bond under the Influence of External Interactions

Grabowski

2015

Crystals

View full text Add to dashboard Cite

“…In the first coordination sphere of F − six FH molecules could be accommodated, while the seventh FH starts to form the second coordination sphere. The structure and properties of [(FH) n F] − clusters were the subject of theoretical and experimental studies …”

Section: Introductionmentioning

confidence: 99%

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

2019

View full text Add to dashboard Cite

The change of cooperativity of FH···Cl− hydrogen bonds upon sequential addition of up to six FH molecules to the Cl− first coordination sphere is investigated. The geometry of clusters [(FH) nCl]− (n = 1…6) was calculated (CCSD/aug‐cc‐pVDZ) and compared with [(FH) nF]− clusters. The geometry is determined by the symmetry‐driven electrostatic requirements and also by the fact that formation of each new FH···Cl− bond creates a depression in the chlorine's electron cloud on the opposite side of Cl− (σ‐hole), which limits the range of directions available for subsequent H‐bond formation. The mutual influence of FH···Cl− hydrogen bonds is anticooperative—the addition of each FH molecule weakens H‐bonds by 23–16% and decreases their covalent character (as seen by LMO‐EDA decomposition and QTAIM analysis). Anticooperativity effects could be tracked by spectroscopic parameters (frequency of local HF mode νFH, chemical shift δH, spin–spin coupling constants 1JFH, 1hJHCl, 2hJFCl and nuclear quadrupolar constants χ18F, χD, and χ35Cl. © 2019 Wiley Periodicals, Inc.

show abstract

Mutual influence of non‐covalent interactions formed by imidazole: A systematic quantum‐chemical study

Shitov,

Krutin,

Tupikina

2024

J Comput Chem

View full text Add to dashboard Cite

Imidazole is a five‐membered heterocycle that is part of a number of biologically important molecules such as the amino acid histidine and the hormone histamine. Imidazole has a unique ability to participate in a variety of non‐covalent interactions involving the NH group, the pyridine‐like nitrogen atom or the π‐system. For many biologically active compounds containing the imidazole moiety, its participation in formation of hydrogen bond NH⋯O/N and following proton transfer is the key step of mechanism of their action. In this work a systematic study of the mutual influence of various paired combinations of non‐covalent interactions (e.g., hydrogen bonds and π‐interactions) involving the imidazole moiety was performed by means of quantum chemistry (PW6B95‐GD3/def2‐QZVPD) for a series of model systems constructed based on analysis of available x‐ray data. It is shown that for considered complexes formation of additional non‐covalent interactions can only enhance the proton‐donating ability of imidazole. At the same time, its proton‐accepting ability can be both enhanced and weakened, depending on what additional interactions are added to a given system. The mutual influence of non‐covalent interactions involving imidazole can be classified as weak geometric and strong energetic cooperativity—a small change in the length of non‐covalent interaction formed by imidazole can strongly influence its strength. The latter can be used to develop methods for controlling the rate and selectivity of chemical reactions involving the imidazole fragment in larger systems. It is shown that the strong mutual influence of non‐covalent interactions involving imidazole is due to the unique ability of the imidazole ring to effectively redistribute electron density in non‐covalently bound systems with its participation.

show abstract

Anticooperativity of FHF hydrogen bonds in clusters of the type F− × (HF)n, RF × (HF)n and XF × (HF)n, R = alkyl and X = H, Br, Cl, F

Cited by 19 publications

References 96 publications

[FHF]−—The Strongest Hydrogen Bond under the Influence of External Interactions

[FHF]−—The Strongest Hydrogen Bond under the Influence of External Interactions

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)

Mutual influence of non‐covalent interactions formed by imidazole: A systematic quantum‐chemical study

Contact Info

Product

Resources

About

Anticooperativity of FHF hydrogen bonds in clusters of the type F− × (HF)n, RF × (HF)n and XF × (HF)n, R = alkyl and X = H, Br, Cl, F

Cited by 19 publications

References 96 publications

[FHF]−—The Strongest Hydrogen Bond under the Influence of External Interactions

[FHF]−—The Strongest Hydrogen Bond under the Influence of External Interactions

Anticooperativity of FH···Cl− hydrogen bonds in [FH)nCl]− clusters (n = 1…6)

Mutual influence of non‐covalent interactions formed by imidazole: A systematic quantum‐chemical study

Contact Info

Product

Resources

About

Anticooperativity of FH···Cl⁻ hydrogen bonds in [FH)_nCl]⁻ clusters (n = 1…6)