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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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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...
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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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Proteins are dynamic macromolecules that carry out a wide variety of essential processes; however, the activities of most proteins depend on their interactions with other molecules or ions, known as ligands.
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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is referred to as its unit cell. The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure then consists of this unit cell repeating in three dimensions. The three different types of unit cells present in the cubic lattice are illustrated in Figure 1.
Types of Unit Cells
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Understanding metal-ligand interactions in coordination polymers using Hirshfeld surface analysis.

Camila B Pinto1, Leonardo H R Dos Santos1, Bernardo L Rodrigues1

  • 1Department of Chemistry, Federal University of Minas Gerais, Avenida Antonio Carlos, 6627, Pampulha, Belo Horizonte - MG, CEP 31270-901, Brazil.

Acta Crystallographica. Section C, Structural Chemistry
|June 6, 2019
PubMed
Summary

Hirshfeld surface analysis, using shape index and curvedness, reveals details of metal-ligand interactions in coordination polymers. This method aids in understanding crystal structures and engineering new materials.

Keywords:
4-nitrophthalic acidHirshfeld surface analysiscoordination polymercrystal engineeringcrystal structurecurvednessphenanthrolineshape index

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Area of Science:

  • Solid-state chemistry
  • Crystallography
  • Materials science

Background:

  • Hirshfeld surfaces offer insights into intermolecular interactions within molecular crystals.
  • Understanding metal-ligand interactions is crucial for coordination polymer design.

Purpose of the Study:

  • To investigate the utility of Hirshfeld surface properties (shape index, curvedness, distances) for analyzing metal-ligand interactions in coordination polymers.
  • To utilize a novel coordination polymer as a model system for this analysis.

Main Methods:

  • Analysis of Hirshfeld surface properties, including shape index (S) and curvedness (C), and distances (de, di).
  • Decomposition of the coordination polymer into metal centers and ligands for individual Hirshfeld surface analysis.
  • Correlation of Hirshfeld surface features with metal-ligand contact geometry.

Main Results:

  • Hirshfeld surface analysis, particularly the shape index, provides detailed information on metal-ligand coordination.
  • The shape of the metal's Hirshfeld surface is sensitive to ligand type and coordination bond length.
  • This approach offers insights beyond conventional crystal packing analysis.

Conclusions:

  • Hirshfeld surface analysis is a powerful tool for understanding metal-ligand interactions in coordination polymers.
  • The method can help estimate coordination distances and establish structure-property relationships for crystal engineering.