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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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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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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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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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¹H NMR: Interpreting Distorted and Overlapping Signals01:02

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Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
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Related Experiment Video

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Near-Infrared Light-Induced Spin-State Switching Based on Fe(II)-Hg(II) Spin-Crossover Network.

Guanping Li1,2, Olaf Stefanczyk1, Kunal Kumar1

  • 1Department of Chemistry, School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.

Angewandte Chemie (International Ed. in English)
|December 11, 2024
PubMed
Summary
This summary is machine-generated.

A new iron(II) spin-crossover (SCO) material exhibits unique near-infrared-responsive light-induced switching. This discovery offers insights into tunable molecular switches and synergistic effects in advanced materials.

Keywords:
Ab Initio CalculationsIron(II) ComplexesPhoto-magnetismSpin-crossoverTerahertz Spectroscopy

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Solid-State Physics

Background:

  • Molecular switches with tunable properties are crucial for advanced applications.
  • Spin-crossover (SCO) materials offer dynamic control over magnetic and optical states.
  • Developing novel SCO materials with unique switching behaviors is an active research area.

Purpose of the Study:

  • To synthesize and characterize a novel iron(II)-based spin-crossover material.
  • To investigate the spin-crossover properties and light-induced phenomena.
  • To explore the synergistic effects in structural, magnetic, and spectroscopic properties.

Main Methods:

  • Synthesis and single-crystal X-ray diffraction of the [Fe(4-acpy)2][Hg(μ-SCN)4] complex.
  • Magnetic, Mössbauer, and photomagnetic measurements.
  • Photocrystallography, optical spectroscopy, terahertz (THz) absorption, and ab initio calculations.

Main Results:

  • A novel 3D coordination network [Fe(4-acpy)2][Hg(μ-SCN)4] was synthesized, crystallizing in the Pna21 space group.
  • An incomplete spin-crossover transition was observed at Fe2 centers with a T1/2 of ~102 K.
  • Light-induced excited spin-state trapping (LIESST) and reverse-LIESST effects were demonstrated, including unique near-infrared responsiveness.
  • Temperature- and light-dependent THz absorptions correlated with SCO behavior and phonon vibrations.

Conclusions:

  • The synthesized Fe(II)-Hg(II) system exhibits distinct SCO behavior and near-infrared light-switchable properties.
  • Photocrystallography confirmed the metastable states associated with LIESST effects.
  • The material serves as a promising benchmark for exploring synergistic switching effects in multifunctional materials.