I127 NQR spectra of fluorinated ?, ?-diiodoalkanes and complexes with amines

Семин, Г. К.; Babushkina, T. A.; Khrlakyan, S. P.; Pervova, E. Ya.; Shokina, V. V.; Knunyants, I. L.

doi:10.1007/bf00525584

Cited by 8 publications

(8 citation statements)

References 4 publications

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“…Already in the early 1970s, the 127 I NQR frequencies of α,ω-diiodoperfluoroalkanes were reported to change in complexes with secondary and tertiary amines, and the effect was attributed to charge-transfer phenomena. 463 A series of NQR studies of trihalide ions 372 and complexes of dihalogens with various amines, including 3,5-dibromopyridine, 464 3,5-dichloropyridine, 465 and trimethylamine, 466 afforded conclusions analogous to those discussed above on the role of charge-transfer phenomena in the formation of complexes.…”

Section: Chemical Reviewsmentioning

confidence: 85%

The Halogen Bond

et al. 2016

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The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

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Section: Chemical Reviewsmentioning

confidence: 85%

The Halogen Bond

et al. 2016

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“…NQR studies have been performed on halogen bonded compounds. − Solid-state NMR of 35 Cl boasts some advantages over pure 35 Cl NQR, such as being able to simultaneously measure both C Q and η in a single one-dimensional spectrum on a powdered sample. Although the NMR spectra are broad (several MHz), one does not have to search for the resonance frequency.…”

Section: Introductionmentioning

confidence: 99%

³⁵Cl Solid-State NMR and Computational Study of Chlorine Halogen Bond Donors in Single-Component Crystalline Chloronitriles

Szell

Bryce

2016

J. Phys. Chem. C

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Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor, which has gained popularity in the field of crystal engineering due to its strength and linearity. Here, we present a 35Cl solid-state NMR study of chlorine atoms as halogen bond donors, with interpretation aided by crystallographic symmetry and computational chemistry. In a series of chlorinated benzonitrile compounds, the magnitude of the 35Cl quadrupolar coupling constant (C Q) was found to increase, and the quadrupolar asymmetry parameter (η) was found to decrease upon halogen bonding. A natural localized molecular orbital (NLMO) analysis attributes these changes to an increase in the contribution from the lone pair NLMOs to |C Q|. This is distinguished from a short proton-chlorine contact, which causes an increase in the magnitude of the σ-bond contribution and a decrease in the lone pair contribution, resulting in an overall decrease in |C Q|. This first direct 35Cl solid-state NMR study of chlorine as a halogen bond donor provides new physical insight into the relationship between NMR observables and the halogen bond.

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“…However, in contrast to our results, a 1968 report investigating complexes claimed to be formed between diiodoalkanes and amines by 127 I NQR reported a decrease in the NQR frequency by 6.8 MHz. The authors proposed a C−I⋅⋅⋅N motif resembling a halogen bond . However, without support from X‐ray results, it is difficult to conclusively deduce the structural motif solely by NQR shifts.…”

Section: Resultsmentioning

confidence: 99%

Rapid Identification of Halogen Bonds in Co‐Crystalline Powders via ¹²⁷I Nuclear Quadrupole Resonance Spectroscopy

2019

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127I nuclear quadrupole resonance (NQR) spectroscopy is established as a rapid and robust method to indicate the formation of iodine–nitrogen halogen bonds in co‐crystalline powders. Once the relevant spectral frequency range has been established, diagnostic 127I NQR spectra can be acquired in seconds. The method is demonstrated for a series of co‐crystals of 1,4‐diiodobenzene. Changes in the 127I quadrupolar coupling constant (CQ) by up to 74.4 MHz correlate with the length of the C−I donor covalent bond and inversely with the I⋅⋅⋅N halogen‐bond length. The predictive power of this technique is validated on two previously unknown co‐crystalline powders prepared mechanochemically. Single‐crystal growth via co‐sublimation and structure determination by single‐crystal X‐ray diffraction cross‐validates the findings. Natural localized molecular‐orbital analyses provide insight into the origins of the quadrupolar coupling constants.

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I127 NQR spectra of fluorinated ?, ?-diiodoalkanes and complexes with amines

Cited by 8 publications

References 4 publications

The Halogen Bond

The Halogen Bond

³⁵Cl Solid-State NMR and Computational Study of Chlorine Halogen Bond Donors in Single-Component Crystalline Chloronitriles

Rapid Identification of Halogen Bonds in Co‐Crystalline Powders via ¹²⁷I Nuclear Quadrupole Resonance Spectroscopy

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I127 NQR spectra of fluorinated ?, ?-diiodoalkanes and complexes with amines

Cited by 8 publications

References 4 publications

The Halogen Bond

The Halogen Bond

35Cl Solid-State NMR and Computational Study of Chlorine Halogen Bond Donors in Single-Component Crystalline Chloronitriles

Rapid Identification of Halogen Bonds in Co‐Crystalline Powders via 127I Nuclear Quadrupole Resonance Spectroscopy

Contact Info

Product

Resources

About

³⁵Cl Solid-State NMR and Computational Study of Chlorine Halogen Bond Donors in Single-Component Crystalline Chloronitriles

Rapid Identification of Halogen Bonds in Co‐Crystalline Powders via ¹²⁷I Nuclear Quadrupole Resonance Spectroscopy