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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...

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...

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...

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.

Network Covalent Solids

Network Covalent Solids

Network covalent solids contain a three-dimensional network of covalently bonded atoms as found in the crystal structures of nonmetals like diamond, graphite, silicon, and some covalent compounds, such as silicon dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds.
To break or to melt a covalent network solid, covalent bonds must be broken. Because covalent bonds are relatively strong, covalent network solids are typically...

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...

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Related Experiment Video

Updated: Aug 22, 2025

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

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Published on: May 12, 2023

Bis(Vinylenedithio)-Tetrathiafulvalene-Based Coordination Networks.

Federica Solano¹, Pascale Auban-Senzier², Iwona Olejniczak³

¹Univ Angers, CNRS, MOLTECH-ANJOU, SFR MATRIX, 49000, Angers, France.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|November 9, 2022

Summary

Researchers developed novel sulfur-rich coordination polymers using bis(vinylenedithio)-tetrathiafulvalene (BVDT-TTF) ligands. These materials exhibit enhanced conductivity after iodine oxidation, paving the way for advanced porous conducting materials.

Keywords:

Raman spectroscopy X-ray diffraction conducting materials crystal engineering metal-organic frameworks

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Area of Science:

Materials Science
Chemistry
Solid State Physics

Background:

Coordination polymers incorporating electroactive molecules are crucial for developing porous conducting materials.
Tetrathiafulvalene (TTF) based metal-organic frameworks have shown promise for through-space conductivity.
Sulfur-enriched scaffolds for such applications remain underexplored.

Purpose of the Study:

To synthesize and characterize novel coordination polymers using a sulfur-rich bis(vinylenedithio)-tetrathiafulvalene (BVDT-TTF) ligand functionalized with pyridine.
To investigate the impact of chemical oxidation on the conductivity of these novel networks.
To elucidate the electronic structure and conduction mechanism of the synthesized materials.

Main Methods:

Synthesis of coordination polymers using BVDT-TTF and various transition metals.
Chemical oxidation using iodine.
Single-crystal to single-crystal X-ray diffraction for structural analysis.
Raman spectroscopy and Density Functional Theory (DFT) calculations for electronic structure determination.
Band structure calculations to assess conductivity.

Main Results:

Four isostructural coordination polymer networks were successfully synthesized.
Conductivity of the networks significantly increased upon iodine-induced chemical oxidation.
Single-crystal X-ray diffraction confirmed oxidation in the Cd(II) polymer.
DFT and Raman spectroscopy confirmed the oxidation state and electronic properties.
Band structure calculations revealed a 2D conduction mechanism from an antiferromagnetic ground state.

Conclusions:

The study demonstrates the successful incorporation of sulfur-enriched BVDT-TTF ligands into coordination polymers.
Chemical oxidation with iodine effectively enhances the conductivity of these materials.
These findings offer insights into designing improved through-space conducting frameworks using sulfur-rich ligands.