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Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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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.
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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...
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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.
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Chirality is the most intriguing yet essential facet of nature, governing life’s biochemical processes and precision. It can be observed from a snail shell pattern in a macroscopic world to an amino acid, the minutest building block of life. Most of the snails around the world have right-coiled shells because of the intrinsic chirality in their genes. All the amino acids present in the human body exist in an enantiomerically pure state, except for glycine - the sole achiral amino acid.
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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: One-Bond Coupling01:17

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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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奇拉性诱导的旋转轨道合和旋转选择性

Massimiliano Di Ventra1, Rafael Gutierrez2, Gianaurelio Cuniberti2,3

  • 1Department of Physics, University of California San Diego, La Jolla, California 92093, United States.

The journal of physical chemistry. A
|September 30, 2025
PubMed
概括
此摘要是机器生成的。

一条螺旋路径诱导移动的旋转器中的旋转轨道合,解释了奇拉性诱导的旋转选择性 (CISS) 效应. 这种奇拉性诱导的旋转轨道合 (χ-SOC) 是理解螺旋分子中CISS的关键.

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科学领域:

  • 物理 物理学 物理
  • 化学 化学 化学
  • 材料科学 材料科学 材料科学

背景情况:

  • 奇拉性诱导的旋转选择性 (CISS) 效应是一种现象,在这种现象中,奇拉性分子会在电荷载体中诱导旋转极化.
  • 对于CISS效应的微观起源还不完全了解,特别是旋转轨道合的作用.

研究的目的:

  • 为了研究一维螺旋路径中旋转轨道合的出现.
  • 阐明这种合对CISS效应的潜在贡献.

主要方法:

  • 在曲线螺旋路径上对旋转器的行为进行理论分析.
  • 估计由此产生的旋转极化大小.

主要成果:

  • 一个一维的螺旋路径的曲率诱导旋转轨道合在一个旅行的旋转轨道.
  • 估计的旋转极化与表现出CISS效应的性分子结构中观察到的值一致.
  • 奇拉性诱导的旋转轨道合 (χ-SOC),结合破碎的时间逆转对称性,被提议作为CISS的微观基础.

结论:

  • 螺旋轨道的曲率是旋转轨道合的来源.
  • 这种 χ-SOC 机制为奇拉系统中的 CISS 现象提供了潜在的解释.
  • 进一步的研究可以探索这种发现的实验验证和应用.