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NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

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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

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 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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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

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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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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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Molecular electronic spin qubits from a spin-frustrated trinuclear copper complex.

Benjamin Kintzel1, Michael Böhme1, Junjie Liu2

  • 1Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, 07745 Jena, Germany. sekr.plass@uni-jena.de.

Chemical Communications (Cambridge, England)
|October 11, 2018
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Researchers synthesized a novel copper(II) complex exhibiting strong antiferromagnetic coupling, crucial for developing advanced molecular spintronics. This spin-frustrated system shows extended coherence times, making it a promising building block for future electronic devices.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Quantum Computing

Background:

  • Trinuclear copper(II) complexes are investigated for their magnetic properties.
  • Molecular spintronics aims to utilize electron spin for information processing.
  • Spin frustration in magnetic systems can lead to exotic quantum phenomena.

Purpose of the Study:

  • To synthesize and characterize a novel trinuclear copper(II) complex.
  • To investigate the magnetic coupling and spin frustration within the complex.
  • To evaluate the potential of the complex as a building block for molecular spintronics.

Main Methods:

  • Synthesis of [Cu3(saltag)(py)6]ClO4 using tris(2-hydroxybenzylidene)triaminoguanidine ligand.
  • Experimental characterization including magnetic susceptibility measurements.
  • Theoretical calculations to understand electronic structure and magnetic interactions.
  • Measurement of T2 coherence times in frozen pyridine and pyridine-d5 solutions.

Main Results:

  • The complex [Cu3(saltag)(py)6]ClO4 was successfully synthesized and characterized.
  • A strong antiferromagnetic coupling (J = -298 cm-1) was observed, indicating a spin-frustrated system.
  • A T2 coherence time of 340 ns was measured in frozen pyridine, extending to 591 ns in pyridine-d5.

Conclusions:

  • The synthesized copper(II) complex exhibits significant spin frustration due to strong antiferromagnetic coupling.
  • The extended coherence times demonstrate the potential of this compound for quantum information applications.
  • This trinuclear copper(II) complex is a promising candidate for developing molecular spintronics.