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Related Concept Videos

Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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.
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...
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Valence Bond Theory02:42

Valence Bond Theory

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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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Complexation Equilibria: The Chelate Effect01:19

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Crystal Field Theory - Octahedral Complexes02:58

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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.
CFT focuses on...
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Coordination Number and Geometry02:57

Coordination Number and Geometry

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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.
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Complexometric Titration: Ligands00:43

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Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
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Updated: May 4, 2026

Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles
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Programming Palladium Cage Geometry through Ligand Redox Modulation.

Jennifer Bou Zeid1, Jean Nicolas1, Maksym Dekhtiarenko1

  • 1Univ Angers, CNRS, MOLTECH-ANJOU, Angers, France.

Angewandte Chemie (International Ed. in English)
|May 3, 2026
PubMed
Summary
This summary is machine-generated.

Redox-active ligands enable dynamic metal-organic cages. Oxidation state changes reversibly alter cage structure, nuclearity, and composition, offering tunable molecular architectures.

Keywords:
coordination cagesexTTFredoxself‐assemblystimuli‐induced transformations

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Area of Science:

  • Supramolecular Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Redox-active ligands offer tunable properties in coordination chemistry.
  • Metal-organic cages (MOCs) are versatile supramolecular structures with diverse applications.
  • Controlling MOC assembly and properties through external stimuli is a key challenge.

Purpose of the Study:

  • To design and synthesize redox-switchable coordination cages.
  • To investigate how ligand oxidation state influences self-assembly and cage properties.
  • To demonstrate reversible control over MOC nuclearity and composition.

Main Methods:

  • Synthesis of an exTTF-based ditopic ligand (L).
  • Self-assembly of palladium(II) complexes with L to form M2L4 cages.
  • Oxidation of the ligand to L(ox) and subsequent self-assembly into M2L(ox)2 and M2L(ox)L'2 structures.
  • Structural characterization using single-crystal X-ray diffraction.
  • Demonstration of reversible redox-induced transformations.

Main Results:

  • Formation of a M2L4 cage with selective binding for dinitrile alkanes.
  • Oxidation of L to L(ox) redirected self-assembly to a M2L(ox)2 structure.
  • Assembly of a heteroleptic M2L(ox)L'2 structure, which dimerized into an unprecedented M4L4L'4 architecture.
  • Structural authentication of key intermediates and products.
  • Reversible reduction of M2L(ox)L'2 back to the M2L4 cage.

Conclusions:

  • Ligand redox state is a powerful tool for controlling metal-organic assembly.
  • Reversible changes in oxidation state allow for dynamic modulation of MOC nuclearity and composition.
  • This work provides a framework for designing responsive and switchable coordination cages.