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Related Concept Videos

Valence Bond Theory02:42

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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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Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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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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Synthesis and Characterization of Functionalized Metal-organic Frameworks
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Bivariate Metal-Organic Frameworks with Tunable Spin-Crossover Properties.

Yu Gong1, Zhi-Hua Li1, Xiaodong Yan1

  • 1Key Laboratory of Synthetic and Biological Colloids, School of Chemical and Material Engineering, Ministry of Education, Jiangnan University, Wuxi, 214122, P. R. China.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|June 25, 2020
PubMed
Summary

This study constructed novel bivariate metal-organic frameworks (MOFs) with tunable spin-crossover properties. Researchers precisely controlled spin transition temperatures and hysteresis by adjusting ligand proportions in these advanced bistable materials.

Keywords:
Hofmannbivariatehysteresis loopsmetal-organic frameworksspin-crossover

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Area of Science:

  • Materials Science
  • Coordination Chemistry
  • Supramolecular Chemistry

Background:

  • Hofmann-type metal-organic frameworks (MOFs) are promising for advanced materials.
  • Controlling spin-crossover (SCO) properties in MOFs is crucial for bistable applications.
  • Bivariate MOFs offer a route to fine-tune material characteristics.

Purpose of the Study:

  • To construct and characterize bivariate Hofmann-type MOFs using pyrazine derivatives.
  • To investigate the influence of ligand size and crystallization rate on MOF formation.
  • To precisely tune the spin-crossover properties of these bivariate MOFs.

Main Methods:

  • Synthesis of Hofmann-type MOFs using Fe(II) and M(CN)4 (M=Pt, Pd) with pyrazine, aminopyrazine, quinoxaline, and 5,6,7,8-tetrahydroquinoxaline ligands.
  • X-ray single-crystal diffraction to elucidate 3D pillared-layer structures.
  • Characterization using 1H NMR, PXRD, FTIR, and Raman spectroscopy.
  • Analysis of spin-crossover properties by varying ligand ratios and metal centers.

Main Results:

  • Successfully constructed bivariate Hofmann-type MOFs with tunable SCO properties.
  • Demonstrated that ligand size and crystallization rate are key factors in MOF construction.
  • Achieved fine-tuning of spin transition temperatures and hysteresis loop widths by adjusting ligand proportions.
  • Observed significant tunability in SCO properties with both Pt and Pd metal centers.

Conclusions:

  • Ligand selection and proportion are critical for designing bivariate Hofmann-type MOFs with tailored SCO behavior.
  • This work provides a versatile platform for developing advanced bistable materials.
  • Precisely regulating SCO properties through structural modification opens new avenues for materials design.