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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...

Coordination Compounds and Nomenclature

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...

Cationic Chain-Growth Polymerization: Mechanism

Cationic Chain-Growth Polymerization: Mechanism

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...

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.

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...

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...

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Related Experiment Video

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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

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Coordination polymer-forming liquid Cu(2-isopropylimidazolate).

Teerat Watcharatpong¹, Taweesak Pila¹, Thana Maihom²

¹Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology Rayong 21210 Thailand horike@icems.kyoto-u.ac.jp.

Chemical Science

|November 2, 2022

Summary

This summary is machine-generated.

Researchers discovered a novel coordination polymer-forming liquid in molten Cu(isopropylimidazolate). This unique liquid retains coordination bonds above its melting point, exhibiting structures similar to organic polymer melts.

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Area of Science:

Materials Science
Solid-State Chemistry
Polymer Science

Background:

One-dimensional (1D) coordination polymers are crystalline materials with unique properties.
Understanding the behavior of these materials above their melting point is crucial for potential applications.
The melt state of coordination polymers is less understood compared to organic polymers.

Purpose of the Study:

To characterize the melt state structure of the 1D coordination polymer Cu(isopropylimidazolate).
To investigate the preservation of coordination bonds in the melt.
To compare the melt structure to conventional 1D organic polymer melts.

Main Methods:

Differential Scanning Calorimetry (DSC)
Variable temperature Powder X-ray Diffraction (PXRD)
Solid-state Nuclear Magnetic Resonance (SSNMR)
X-ray Absorption Spectroscopy (XAS)
Density Functional Theory-Ab Initio Molecular Dynamics (DFT-AIMD) calculations
Viscoelastic measurements

Main Results:

Formation of a "coordination polymer-forming liquid" above the melting temperature (T_m = 143 °C).
Preservation of coordination bonds in the melt state.
Variable chain configurations and moderate inter-chain cohesive interactions were identified as key factors.
The melt structure showed similarities to entangled or random coil structures found in 1D organic polymer melts.

Conclusions:

Cu(isopropylimidazolate) forms a rare polymer-forming liquid upon melting.
Coordination bonds are stable in the melt, leading to unique liquid-like behavior.
The findings offer insights into the fundamental behavior of 1D coordination polymers in the melt phase.