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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...

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...

Valence Bond Theory

Valence Bond Theory

Overview of Valence Bond Theory

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.

Hydrogen Bonds

Hydrogen Bonds

A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...

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Related Experiment Video

Updated: Nov 6, 2025

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

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

Published on: May 12, 2023

Coordination sphere hydrogen bonding as a structural element in metal-organic Frameworks.

Chris S Hawes¹

¹School of Chemical and Physical Sciences, Keele University, Keele ST5 5BG, UK. c.s.hawes@keele.ac.uk.

Dalton Transactions (Cambridge, England : 2003)

|May 11, 2021

Summary

Researchers explored how hydrogen bonding in metal-organic frameworks (MOFs) can improve stability and predictability. This approach offers new ligand design strategies for creating robust and functional MOFs.

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Last Updated: Nov 6, 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

Synthesis and Characterization of Functionalized Metal-organic Frameworks

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

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Published on: February 10, 2023

Area of Science:

Materials Science
Chemistry
Crystallography

Background:

Designing metal-organic frameworks (MOFs) faces challenges in stability and predictable structures, often limiting ligand choice to conventional dicarboxylates.
A niche group of MOF ligands possess functionalities enabling coordination sphere hydrogen bonding, presenting novel avenues for ligand design.
These hydrogen bonds can enhance the rigidity of mononuclear coordination geometries and improve hydrolytic stability.

Purpose of the Study:

To investigate the role of inner-sphere hydrogen bonding in metal-organic framework (MOF) ligand design.
To explore how pyrazole, amine, amide, and carboxylic acid functionalities influence MOF properties through hydrogen bonding.
To provide insights for leveraging hydrogen bonding in the development of advanced MOF materials.

Main Methods:

Review and analysis of existing literature on MOF ligands containing pyrazole, amine, amide, and carboxylic acid groups.
Examination of coordination sphere hydrogen bonding interactions within these MOF structures.
Correlation of hydrogen bonding effects with overall MOF structure, stability, and function.

Main Results:

Ligands with specific functional groups (pyrazole, amine, amide, carboxylic acid) can engage in inner-sphere hydrogen bonding.
These interactions contribute to the stabilization and rigidity of coordination spheres in MOFs.
Hydrogen bonding positively impacts the hydrolytic stability and functional properties of MOFs.

Conclusions:

Inner-sphere hydrogen bonding is a valuable design principle for creating stable and predictable metal-organic frameworks.
Utilizing ligands with hydrogen-bonding capabilities offers a pathway to overcome current limitations in MOF design.
This perspective provides a foundation for future research in harnessing hydrogen bonding for advanced MOF materials.