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Colors and Magnetism

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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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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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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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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.
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Spin–Spin Coupling Constant: Overview01:08

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1.2K
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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Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
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High-temperature spin crossover in a mononuclear six-coordinate cobalt(II) complex.

Joanna Palion-Gazda1, Anna Świtlicka-Olszewska, Barbara Machura

  • 1Department of Crystallography, Institute of Chemistry, University of Silesia , 9th Szkolna Street, 40006 Katowice, Poland.

Inorganic Chemistry
|September 9, 2014
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Summary

This study reveals a cobalt(II) complex exhibiting thermally induced spin crossover. The material transitions from high-spin to low-spin states below 200 K, demonstrating unique temperature-dependent magnetic properties.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Magnetochemistry

Background:

  • Spin crossover (SCO) materials are of interest for molecular switches and sensors.
  • Cobalt(II) complexes can display spin crossover phenomena.
  • The ligand 2,2′:6′,2″-terpyridine (tppz) and thiocyanate (tcm) are common in coordination chemistry.

Purpose of the Study:

  • To synthesize and characterize a novel six-coordinate cobalt(II) complex.
  • To investigate the spin crossover behavior of the complex [Co(tppz)2](tcm)2.
  • To determine the temperature at which the spin crossover transition occurs.

Main Methods:

  • Synthesis of the cobalt(II) complex [Co(tppz)2](tcm)2.
  • Characterization of the complex using spectroscopic and crystallographic techniques (details not provided in abstract).
  • Variable-temperature magnetic susceptibility measurements to probe spin states.

Main Results:

  • The complex [Co(tppz)2](tcm)2 was successfully synthesized.
  • A thermally induced spin crossover behavior was observed.
  • The transition from a high-spin (S = 3/2) to a low-spin (S = ½) state occurs at or below 200 K.

Conclusions:

  • The cobalt(II) complex [Co(tppz)2](tcm)2 exhibits temperature-dependent spin crossover.
  • The low-spin phase is stable at temperatures ≤ 200 K.
  • This finding contributes to the understanding of SCO materials based on cobalt(II) and terpyridine ligands.