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Structural Isomerism

Structural Isomerism

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...

Valence Bond Theory

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...

Coordination Number and Geometry

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.

Stereoisomerism

Stereoisomerism

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...

Metallic Solids

Metallic Solids

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....

Metal-Ligand Bonds

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...

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Related Experiment Video

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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

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Published on: August 2, 2012

Controlling the Formation of Two Concomitant Polymorphs in Hg(II) Coordination Polymers.

Francisco Sánchez-Férez¹, Xavier Solans-Monfort¹, Teresa Calvet²

¹Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.

Inorganic Chemistry

|March 17, 2022

Summary

Crystal engineering enables control over crystalline forms. Researchers selectively synthesized two polymorphs of a mercury compound, {[Hg(Pip)2(4,4′-bipy)]·DMF}, by altering synthesis conditions, revealing differences in stability and photoluminescence.

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Published on: February 7, 2017

Area of Science:

Crystal Engineering
Coordination Chemistry
Materials Science

Background:

Controlling crystalline form is crucial in crystal engineering.
Polymorphism, arising from different molecular arrangements, presents significant challenges in synthesis and characterization.
Understanding the factors governing preferential polymorph formation is key to targeted material design.

Purpose of the Study:

To achieve selective synthesis of two concomitant polymorphs of {[Hg(Pip)2(4,4′-bipy)]·DMF}.
To investigate the structural differences and stability of the observed polymorphs.
To correlate structural variations with solid-state photoluminescence properties.

Main Methods:

Selective synthesis by modifying reaction conditions.
Characterization using unit cell measurements and decomposition temperature analysis.
Crystal structure elucidation and Density Functional Theory (DFT) calculations.

Main Results:

Two polymorphs, P1A and P1B, of {[Hg(Pip)2(4,4′-bipy)]·DMF} were selectively synthesized.
Structural analysis revealed differences in Hg(II) core arrangements and intermolecular interactions (Hg···π, π···π).
DFT calculations indicated P1B is more stable than P1A due to enhanced interchain interactions, leading to varied photoluminescence.

Conclusions:

Selective synthesis of polymorphs is achievable by controlling reaction parameters.
Polymorphism in this mercury complex is influenced by metal-ligand coordination and non-covalent interactions.
Structural differences directly impact solid-state photoluminescence, offering avenues for tuning material properties.