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Valence Bond Theory

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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...

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Complexation Equilibria: Overview

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Complexation reactions take place when dative or coordinate covalent bonds form between metal ions and ligands. The compounds formed in these reactions are called coordination compounds. The number of bonds formed between the metal ion and the ligands is called its coordination number. Generally, most metal ions in an aqueous solution are solvated by water molecules and thus exist as aqua complexes.
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Complexation Equilibria: Factors Influencing Stability of Complexes

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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...

Complexation Equilibria: The Chelate Effect

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...

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Related Experiment Video

Updated: Mar 2, 2026

Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides

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Published on: September 7, 2019

Coevolution and ratiometric behaviour in metal cation-driven dynamic covalent systems.

Sébastien Dhers¹, Jan Holub¹, Jean-Marie Lehn¹

¹Laboratoire de Chimie Supramoléculaire , ISIS , Université de Strasbourg , 8 Allée Gaspard Monge , 67000 Strasbourg , France .

Chemical Science

|May 17, 2017

Summary

Dynamic Covalent Libraries (DCLs) demonstrate molecular coevolution. Two systems show how metal ions and dynamic molecules create selective, synergistic outcomes, simplifying complex mixtures through co-evolution.

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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides

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Published on: December 16, 2013

Area of Science:

Supramolecular Chemistry
Chemical Systems Biology
Materials Science

Background:

Dynamic Covalent Libraries (DCLs) utilize reversible covalent bonds for adaptive molecular systems.
Constitutional Dynamic Networks (CDNs) offer a framework for creating complex molecular architectures from dynamic components.
Coevolutionary principles can be applied to molecular systems to achieve emergent complexity and selectivity.

Purpose of the Study:

To demonstrate molecular coevolution using dynamic covalent molecules like imines and hydrazones.
To investigate the formation of Constitutional Dynamic Networks (CDNs) with metal ion complexation.
To explore synergistic and antagonistic behaviors in multi-component dynamic systems.

Main Methods:

Synthesis and characterization of macrocyclic bis-imines from dialdehydes and diamines.
Complexation studies involving Zn(II), Hg(II), and Cu(I) metal ions with dynamic ligands.
Analysis of system evolution and selectivity under varying conditions, including simultaneous and sequential metal ion addition.

Main Results:

Formation of a 2x2 CDN of four macrocyclic bis-imine complexes with Zn(II) and Hg(II).
Demonstration of selective metal-ligand complexation, where combined cations yield a simpler, more selective outcome than individual cations.
Observation of metalloselection and correlated evolution in a four-component system (2 amines, 2 aldehydes) with Zn(II) and Cu(I).
Evidence of dynamic ratiometry linked to antagonistic ligand behavior.

Conclusions:

Dynamic Covalent Libraries can exhibit coevolutionary behavior, leading to simplified and selective outcomes.
Metal ion complexation within CDNs can drive synergistic coevolution, overcoming initial complexity.
The study highlights the potential of DCLs for designing responsive and selective molecular systems.