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Related Concept Videos

Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

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Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
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Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

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Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
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Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

1.5K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
1.5K
NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

3.3K
The spin state of an NMR-active nucleus can have a slight effect on its immediate electronic environment. This effect propagates through the intervening bonds and affects the electronic environments of NMR-active nuclei up to three bonds away; occasionally, even farther. This phenomenon is called spin–spin coupling or J-coupling. Coupling interactions are mutual and result in small changes in the absorption frequencies of both nuclei involved. While nuclei of the same element are involved...
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Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

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In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
1.5K
Atomic Nuclei: Nuclear Spin01:08

Atomic Nuclei: Nuclear Spin

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All atomic particles possess an intrinsic angular momentum, or 'spin'. Electrons, protons, and neutrons each have a spin value of ½, although protons and neutrons in nuclei may have higher half-integer spins owing to energetic factors.
Atomic nuclei have a net nuclear spin, , which can have an integer or half-integer value. In atomic nuclei, the spins of protons are paired against each other but not with neutrons, and vice versa. Consequently, an even number of protons does not contribute to...
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High-Temperature and High-Pressure In situ Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy
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Unusual Indirect Nuclear Spin-Spin Exchange Coupling through Solvated Electron.

Changzhe Zhang1, Qi Luo1, Shibo Cheng1

  • 1School of Chemistry and Chemical Engineering, Shandong University , Jinan, 250100, People's Republic of China.

The Journal of Physical Chemistry Letters
|January 26, 2018
PubMed
Summary

Solvated electrons trigger indirect nuclear spin-spin J-coupling between distant nuclei, mediated by the electron itself rather than bonds. This discovery offers new insights into electron-mediated interactions.

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Area of Science:

  • Quantum Chemistry
  • Physical Chemistry
  • Condensed Matter Physics

Background:

  • Solvated electrons exhibit unique properties like superconductivity.
  • Their influence on nuclear spin properties remains largely unexplored.
  • Understanding electron-mediated interactions is crucial for novel material applications.

Purpose of the Study:

  • To investigate solvated-electron-triggered indirect nuclear spin-spin J-coupling.
  • To explore the mechanism of J-coupling mediated by solvated electrons.
  • To analyze the factors influencing the coupling magnitude.

Main Methods:

  • Density functional theory (DFT) calculations.
  • Utilizing fluorine-19 (19F) as a probe nucleus.
  • Analyzing HF-containing anionic clusters.

Main Results:

  • Confirmed unusual J-couplings between distant 19F atoms in HF clusters.
  • Demonstrated J-coupling mediated through solvated electrons, not conventional bonds.
  • Identified solvated electrons as efficient long-range J-coupling channels due to dispersivity and Rydberg character.

Conclusions:

  • Solvated electrons provide a novel pathway for long-range nuclear spin-spin J-coupling.
  • The coupling strength is sensitive to electron distribution and electron-solvating unit interactions.
  • This research opens avenues for applications utilizing weakly bound electrons.