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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...

Spin–Spin Coupling: One-Bond Coupling

Spin–Spin Coupling: One-Bond Coupling

Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...

Spin–Spin Coupling Constant: Overview

Spin–Spin Coupling Constant: Overview

In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must have a...

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...

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...

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Related Experiment Video

Updated: Jun 21, 2026

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Published on: February 10, 2023

Dynamic interplay between spin-crossover and host-guest function in a nanoporous metal-organic framework material.

Peter D Southon¹, Lang Liu, Elizabeth A Fellows

¹School of Chemistry, The University of Sydney, NSW 2006, Australia.

Journal of the American Chemical Society

|July 23, 2009

Summary

This study introduces a robust metal-organic framework that exhibits spin-crossover behavior. The material

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Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

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Published on: February 10, 2023

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Synthesis and Characterization of Functionalized Metal-organic Frameworks

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Determining Surface Areas and Pore Volumes of Metal-Organic Frameworks

Determining Surface Areas and Pore Volumes of Metal-Organic Frameworks

Published on: March 8, 2024

Area of Science:

Materials Science
Chemistry
Nanotechnology

Background:

Metal-organic frameworks (MOFs) are versatile porous materials with tunable properties.
Spin-crossover (SCO) materials exhibit a reversible switch between low-spin and high-spin states.
Understanding the interplay between guest molecules and SCO behavior in MOFs is crucial for developing advanced functional materials.

Purpose of the Study:

To investigate the spin-crossover properties of a nanoporous metal-organic framework, [Fe(pz)Ni(CN)(4)], 1.
To explore the influence of guest molecule adsorption and desorption on the SCO behavior.
To examine the impact of SCO on the host-guest properties of the MOF.

Main Methods:

Synthesis and structural characterization of the [Fe(pz)Ni(CN)(4)], 1 MOF.
Gas and vapor adsorption/desorption studies.
Variable-temperature magnetic susceptibility measurements to probe spin-crossover transitions.
Analysis of structure-property relationships.

Main Results:

The MOF [Fe(pz)Ni(CN)(4)], 1 displays hysteretic spin-crossover at ambient conditions.
Guest molecule adsorption/desorption significantly influences SCO behavior, with larger guests stabilizing the high-spin state.
The SCO state modulates the MOF's affinity for guest molecules, demonstrating a dynamic interplay.
The material exhibits chemisensing capabilities and a guest-dependent memory effect.

Conclusions:

The pillared Hofmann system [Fe(pz)Ni(CN)(4)], 1 exhibits unique bidirectional control between spin-crossover and host-guest properties.
This MOF demonstrates potential for applications in sensing and memory devices due to its tunable and switchable characteristics.
The findings highlight the importance of guest-host interactions in designing responsive MOF-based materials.