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Related Concept Videos

Valence Bond Theory02:45

Valence Bond Theory

Overview of Valence Bond Theory
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...
Colors and Magnetism03:02

Colors and Magnetism

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 eye.
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: 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,...
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...

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Related Experiment Video

Updated: May 10, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
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Halogen-Driven Spin Dynamics: Exploring Correlation of Cooperativity and Spin Crossover in Solid-State Mononuclear

Li-Wen Chen1, Hai Zhu1, Hua-Wei Zhou1

  • 1State Key Laboratory of Flexible Electronics (LoFE) & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China.

Inorganic Chemistry
|March 28, 2025
PubMed
Summary

We synthesized four new iron(III) complexes with halogen-substituted ligands. Complex 2 shows a unique two-step spin crossover, demonstrating how halogens influence magnetic properties in spin crossover (SCO) materials.

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Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
06:53

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Published on: June 9, 2023

Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Magnetism

Background:

  • Spin crossover (SCO) materials are of interest for molecular switches and sensors.
  • Tuning SCO properties requires understanding ligand effects on metal centers.
  • Iron(III) complexes offer a platform for studying spin state transitions.

Purpose of the Study:

  • Synthesize and characterize novel mononuclear iron(III) complexes.
  • Investigate the influence of halogen substituents on SCO behavior.
  • Elucidate the relationship between crystal structure and magnetic properties.

Main Methods:

  • Synthesis of four [Fe(5-X-sal2trien)]ReO4 complexes (X = F, Cl, Br, I).
  • Magnetic susceptibility measurements to determine spin states and transitions.
  • Single-crystal X-ray diffraction at variable temperatures to analyze structural changes.

Main Results:

  • Complex 1 (X=F) remains high-spin.
  • Complexes 3 (X=Br) and 4 (X=I) show gradual spin crossover above 300 K.
  • Complex 2 (X=Cl) exhibits a two-step spin crossover at 250 K and 209 K with structural phase transitions (Pccn-Pmmn-P21/m).

Conclusions:

  • Halogen substituents significantly impact the cooperativity and magnetic properties of iron(III) SCO complexes.
  • The observed two-step SCO in complex 2 is linked to distinct structural phase transitions.
  • This study provides insights into designing SCO materials with tailored properties.