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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)

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...
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,...
Valence Bond Theory02:42

Valence Bond Theory

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...
Chair Conformation of Cyclohexane02:02

Chair Conformation of Cyclohexane

The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this staggered...
Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

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 have a...
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...

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Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
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Dynamic structural conversion in a spin-crossover cobalt(ii) compound with long alkyl chains.

Shinya Hayami1, Kazuhisa Murata, Daisuke Urakami

  • 1Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, 739-8526, Japan. hayami@hiroshima-u.ac.jp

Chemical Communications (Cambridge, England)
|December 6, 2008
PubMed
Summary

A new cobalt compound with long alkyl chains shows unique spin crossover behavior. This spin transition occurs at specific temperatures with a notable hysteresis, linked to molecular motion.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Spin crossover (SCO) materials are of interest for molecular switches and sensors.
  • Designing SCO compounds with tunable transition temperatures and hysteresis is crucial for practical applications.
  • The influence of long alkyl chains on SCO properties requires further investigation.

Purpose of the Study:

  • To synthesize and characterize a novel cobalt(II) compound featuring long alkyl chains.
  • To investigate the spin crossover (SCO) properties of the synthesized compound.
  • To explore the relationship between the long alkyl chains' motion and the observed spin transition.

Main Methods:

  • Synthesis of the cobalt(II) compound [Co(C14-terpy)(2)](BF(4))(2).MeOH.
  • Variable-temperature magnetic susceptibility measurements to detect spin transitions.
  • Analysis of structural changes accompanying the spin transition.

Main Results:

  • The cobalt(II) compound [Co(C14-terpy)(2)](BF(4))(2).MeOH (1) was successfully prepared.
  • Unique spin crossover (SCO) was observed at T(1) = 50 K.
  • A distinct spin transition occurred at T(2)↑ = 206 K and T(2)↓ = 184 K, exhibiting a hysteresis of ΔT = 22 K.
  • The spin transition was accompanied by the motion of the long alkyl chains.

Conclusions:

  • The synthesized cobalt(II) complex displays complex spin crossover behavior.
  • The presence of long alkyl chains significantly influences the SCO properties, including hysteresis.
  • The observed hysteresis is linked to the cooperative motion of the alkyl chains, suggesting potential for molecular device applications.