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Related Concept Videos

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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¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

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The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
1.9K
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

1.1K
Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
1.1K
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...
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Double Resonance Techniques: Overview01:12

Double Resonance Techniques: Overview

254
Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or radiofrequency pulses to manipulate and observe two distinct nuclear spins. One important application of double resonance is spin decoupling, which selectively suppresses coupling with one type of nucleus while observing the NMR signal from another nucleus, simplifying the spectrum and enhancing resolution.
Spin decoupling is usually achieved by...
254
NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

1.5K
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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Tunable Interferometric Effects between Single-Molecule Suzuki-Miyaura Cross-Couplings.

Yilin Guo1, Chen Yang1, Lei Zhang1

  • 1Beijing National Laboratory for Molecular Sciences, National Biomedical Imaging Center, College of Chemistry and Molecular Engineering, Peking University, 292 Chengfu Road, Haidian District, Beijing 100871, P. R. China.

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This study reveals how multiple catalysts interact at the single-molecule level, uncovering complex reaction dynamics. It bridges the gap between observing individual molecules and understanding bulk chemical reactions.

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Area of Science:

  • Single-molecule spectroscopy
  • Catalysis
  • Nanotechnology

Background:

  • Understanding catalytic processes at the single-molecule level is crucial for advancing chemical reactions.
  • Extrapolating single-molecule behavior to ensemble properties remains a significant challenge in chemistry.

Purpose of the Study:

  • To investigate the cross-correlation and emergent complexity between multiple catalysts in a single device.
  • To demonstrate a novel method for measuring reaction dynamics at the single-event level for multiple molecules.

Main Methods:

  • Integration of two molecular bridges loaded with palladium catalysts into graphene electrodes.
  • Utilizing single-molecule electrical spectroscopy to analyze catalytic pathways.
  • Observing Suzuki-Miyaura cross-coupling reactions at the single-molecule level.

Main Results:

  • Mapped cross-correlations between different palladium catalysts.
  • Revealed anticorrelation behaviors between catalysts due to solvent-induced dipole-dipole interactions and destructive interference.
  • Observed cooperative coupling leading to local acceleration of elementary steps.

Conclusions:

  • Developed a method to study multi-catalyst interactions with single-event resolution.
  • Demonstrated emergent complexity arising from the interplay of multiple catalysts.
  • Established a new approach to bridge the gap between single-molecule and ensemble reaction dynamics.