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Chirality at Nitrogen, Phosphorus, and Sulfur02:30

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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
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Three-Dimensional Chiral Metal-Organic Frameworks: Synthesis and Structural Transformations.

Vadim A Dubskikh1, Anna A Lysova1, Denis G Samsonenko1

  • 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., Novosibirsk 630090, Russia.

Nanomaterials (Basel, Switzerland)
|January 9, 2026
PubMed
Summary
This summary is machine-generated.

Four new chiral porous metal-organic frameworks (MOFs) exhibit reversible, solvent-induced structural changes and selective adsorption. These properties highlight their potential for stereoselective applications in molecular separation.

Keywords:
benzene and cyclohexane separationchiral coordination polymersmetal–organic frameworkstructural transformation

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Area of Science:

  • Materials Science
  • Coordination Chemistry
  • Supramolecular Chemistry

Background:

  • Metal-organic frameworks (MOFs) are crystalline materials with tunable porosity.
  • Chiral MOFs are of interest for enantioselective separations and catalysis.
  • Understanding framework dynamics and guest-host interactions is crucial for MOF applications.

Purpose of the Study:

  • To synthesize and characterize new porous homochiral metal-organic frameworks (MOFs).
  • To investigate the solvent-induced dynamics and thermal stability of these MOFs.
  • To evaluate their potential for size-selective molecular adsorption and separation.

Main Methods:

  • Synthesis of four new homochiral MOFs: [M₂(camph)₂(bpa)]∙Solv (M = Co(II), Ni(II), Cu(II), Zn(II)).
  • Structural characterization using single-crystal and powder X-ray diffraction.
  • Thermal stability analysis, solvent-induced dynamics investigation, and 1H NMR spectroscopy for adsorption studies.

Main Results:

  • Four isostructural porous homochiral MOFs were successfully synthesized and characterized.
  • Frameworks exhibited reversible, solvent-induced transitions between open and non-porous phases.
  • The Zn(II) MOF demonstrated size-selective adsorption, preferentially binding smaller benzene over larger cyclohexane.

Conclusions:

  • The synthesized chiral MOFs possess dynamic frameworks with tunable porosity.
  • High framework stability and selective adsorption capabilities suggest utility in stereoselective applications.
  • These MOFs show promise for advanced molecular separation technologies.