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Structural Isomerism02:34

Structural Isomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
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Stereoisomerism02:52

Stereoisomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Metallic Solids02:37

Metallic Solids

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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
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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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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

515
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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Properties of Organometallic Compounds01:23

Properties of Organometallic Compounds

996
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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Synthesis of a Water-soluble Metal&#8211;Organic Complex Array
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Cross-catenation between position-isomeric metallacages.

Yiliang Wang1, Taotao Liu1, Yang-Yang Zhang2

  • 1State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin, 541004, PR China.

Nature Communications
|February 14, 2024
PubMed
Summary

Researchers created a novel cross-catenated structure using two platinum(II) metallacages. This complex assembly, formed selectively in crystals, offers new insights into controlling intricate hierarchical self-assembly systems.

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Area of Science:

  • Supramolecular Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Hierarchical assembly of complex structures is crucial for advanced materials.
  • Controlling the formation of low-symmetry, high-complexity systems remains a challenge.
  • Cross-catenated metallacages are underexplored supramolecular systems.

Purpose of the Study:

  • To synthesize and characterize a cross-catenated assembly from two distinct platinum(II) metallacages.
  • To investigate the solution behavior and thermodynamic stability of these assemblies.
  • To provide insights into the selective formation of complex hierarchical structures.

Main Methods:

  • Synthesis of position-isomeric platinum(II) metallacages.
  • Solution characterization using variable temperature nuclear magnetic resonance (VT-NMR) and time-of-flight mass spectrometry (TOF-MS).
  • Crystallization studies and density functional theory (DFT) calculations for structural analysis.

Main Results:

  • Formation of [2]catenanes in solution from individual metallacages.
  • Selective crystallization of a 1:1 cross-catenane from a mixture of two metallacages.
  • DFT calculations revealed higher binding energy for cross-catenanes, indicating thermodynamic control over crystallization.

Conclusions:

  • Demonstrated the selective formation of a cross-catenated assembly between two different metallacages.
  • Established that the selectivity of cross-catenane crystallization is thermodynamically driven.
  • This work offers a facile approach for designing low-symmetry, high-complexity self-assembled systems.