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Related Concept Videos

NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

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

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

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...
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

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

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

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...
Atomic Nuclei: Magnetic Resonance01:05

Atomic Nuclei: Magnetic Resonance

The number of nuclear spins aligned in the lower energy state is slightly greater than those in the higher energy state. In the presence of an external magnetic field, as the spins precess at the Larmor frequency, the excess population results in a net magnetization oriented along the z axis. When a pulse or a short burst of radio waves at the Larmor frequency is applied along the x axis, the coupling of frequencies causes resonance and flips the nuclear spins of the excess population from the...
Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

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 Saturation Transfer Difference NMR (SSTD NMR): A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes
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Published on: November 12, 2016

Magnetic exchange coupling in actinide-containing molecules.

Jeffrey D Rinehart1, T David Harris, Stosh A Kozimor

  • 1Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.

Inorganic Chemistry
|April 14, 2009
PubMed
Summary

Researchers are exploring actinide coordination clusters for stronger magnetic exchange interactions, potentially leading to new single-molecule magnets. This study focuses on uranium-containing systems and methods to analyze their magnetic properties.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Magnetism

Background:

  • Actinide coordination clusters are emerging systems for studying magnetic exchange coupling.
  • 5f electrons in actinides offer potential for stronger magnetic exchange than lanthanide 4f electrons.
  • Understanding actinide magnetism is crucial for developing new magnetic materials.

Purpose of the Study:

  • To survey actinide-containing molecules exhibiting magnetic exchange interactions.
  • To investigate methods for interpreting complex magnetic susceptibility data in actinide compounds.
  • To explore the potential of modular synthesis for tuning magnetic properties in actinide clusters.

Main Methods:

  • Survey of multiuranium, uranium-lanthanide, uranium-transition metal, and uranium-radical species.
  • Application of a data subtraction approach using diamagnetic analogues.
  • Estimation of exchange constants from magnetic susceptibility data.
  • Evaluation of linear clusters (cyclam)M[(mu-Cl)U(Me(2)Pz)(4)](2) for magnetic exchange.

Main Results:

  • Identified actinide-containing molecules exhibiting magnetic exchange interactions.
  • Demonstrated a data subtraction method to probe exchange coupling in complex systems.
  • Observed strong ferromagnetic exchange (15 cm(-1) < J < 48 cm(-1)) in Co(II)-containing linear clusters.
  • Highlighted the modularity of these systems for tuning magnetic properties.

Conclusions:

  • Actinide coordination clusters show promise for stronger magnetic exchange.
  • Developed methods aid in understanding and quantifying magnetic coupling in these systems.
  • Modular synthesis offers a pathway to design novel actinide-based magnetic materials and single-molecule magnets.