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Related Concept Videos

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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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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Valence Bond Theory

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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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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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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 Constant: Overview01:08

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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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NMR Spectroscopy: Spin–Spin Coupling01:08

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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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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
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Three-Step Spin Crossover in a Pseudo-3D Hofmann-Type Complex Originating from Anisotropic Supramolecular

Xiaochun Li1, Nour-El-Islam Belmouri2, Mouhamadou Sy2,3

  • 1Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, 1348 Louvain-la-Neuve, Belgium.

Journal of the American Chemical Society
|December 3, 2025
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Summary

Researchers developed a novel 2D Hofmann-like material exhibiting a three-step spin crossover. This discovery advances molecular information processing and sensing applications through tailored supramolecular interactions.

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Supramolecular Chemistry

Background:

  • Multistep spin crossover materials are crucial for molecular information processing and sensing.
  • Synthesizing and understanding these materials presents significant challenges.

Purpose of the Study:

  • To introduce the first iron(II) two-dimensional Hofmann structure incorporating 1,2,4-triazole derivatives and [Au(CN)2]- units.
  • To investigate the spin crossover behavior and underlying mechanisms of the novel material.

Main Methods:

  • Synthesis of the iron(II) complex Fe(MeOPhtrz)2[Au(CN)2]2.
  • Characterization using magnetic susceptibility, differential scanning calorimetry, Raman spectroscopy, single-crystal X-ray diffraction (SXRD), and optical microscopy.
  • Analysis of supramolecular interactions and crystallographic data.

Main Results:

  • The synthesized complex exhibits a temperature-induced three-step spin crossover behavior.
  • SXRD revealed a pseudothree-dimensional structure stabilized by hydrogen bonding, π-π stacking, and π-Au interactions.
  • Anisotropic supramolecular framework and differential rigidity along crystallographic axes contribute to the multistep spin transition.

Conclusions:

  • Supramolecular interactions play a critical role in controlling spin crossover properties in 2D Hofmann-like materials.
  • This work opens new pathways for designing functional 2D materials with tunable spin crossover characteristics.