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Related Concept Videos

Coordination Number and Geometry02:57

Coordination Number and Geometry

For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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...
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Coordination Compounds and Nomenclature02:54

Coordination Compounds and Nomenclature

In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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.
CFT focuses on...

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Updated: Jun 21, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Polynuclear coordination cages.

Michael D Ward1

  • 1Department of Chemistry, University of Sheffield, Sheffield, UKS3 7HF. m.d.ward@sheffield.ac.uk

Chemical Communications (Cambridge, England)
|July 21, 2009
PubMed
Summary
This summary is machine-generated.

Self-assembly of transition metal dications with bis-bidentate ligands forms polyhedral cage complexes. These structures exhibit host-guest properties, anion templating, and tunable fluorescence due to aromatic stacking.

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Area of Science:

  • Coordination Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Transition metal ions and chelating ligands are fundamental building blocks in coordination chemistry.
  • Self-assembly offers a powerful route to construct complex supramolecular architectures.
  • Polyhedral cage complexes have garnered interest for their unique structural and functional properties.

Purpose of the Study:

  • To investigate the self-assembly of six-coordinate transition metal dications with bis-bidentate pyrazolyl-pyridine ligands.
  • To characterize the resulting polyhedral cage complexes and explore their structural diversity.
  • To examine the properties of these self-assembled cages, including templating, host-guest interactions, and fluorescence.

Main Methods:

  • Reaction of metal dications with bis-bidentate ligands.
  • Structural characterization of self-assembled complexes using X-ray crystallography.
  • Investigation of cage properties such as anion templating and host-guest behavior.
  • Incorporation of fluorophores into ligand backbones to study fluorescence properties.

Main Results:

  • Formation of diverse polyhedral cage complexes including M(4)L(6) tetrahedra, M(8)L(12) cubes, and M(12)L(18) truncated tetrahedra.
  • Established a consistent metal:ligand ratio of 2:3 for six-coordinate metals and tetradentate ligands.
  • Observed anion-based template effects, host-guest chemistry, and stability enhancement via peripheral aromatic stacking.
  • Demonstrated modified fluorescence properties linked to aromatic stacking of fluorophores.

Conclusions:

  • Bis-bidentate ligands effectively direct the self-assembly of transition metals into discrete polyhedral cages.
  • The observed structures are predictable based on vertex-to-face ratios of polyhedra.
  • The cages possess tunable properties relevant for host-guest chemistry and sensing applications.
  • Complex structures like M(12) cuboctahedra can be accessed using mixed ligand strategies.