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Related Concept Videos

Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

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 Effect01:19

Complexation Equilibria: The Chelate Effect

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...
Formation of Complex Ions03:45

Formation of Complex Ions

A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
Ionic Association01:28

Ionic Association

The ionic association is the association of oppositely charged ions in an electrolyte solution to form ion pairs. Bjerrum defined ion pairs as two oppositely charged ions whose electrostatic attraction exceeds the thermal energy of the system, typically expressed as 2kT. Electrostatic attraction depends on ionic charge, separation distance, and the dielectric constant of the medium. Thermal energy, represented by kT, reflects the tendency of ions to move independently due to molecular motion.
Complexation Equilibria: Overview01:23

Complexation Equilibria: Overview

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.
The equilibrium constant of the complexation reaction is represented as the formation constant...
EDTA: Chemistry and Properties01:22

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Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...

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Anion-complexation-induced stabilization of charge separation.

Francis D'Souza1, Navaneetha K Subbaiyan, Yongshu Xie

  • 1Department of Chemistry, Wichita State University, 1845 Fairmount, Wichita, Kansas 67260-0051, USA. Francis.DSouza@wichita.edu

Journal of the American Chemical Society
|November 6, 2009
PubMed
Summary

Anion binding to a supramolecular system stabilizes the charge-separated state, significantly extending its lifetime. This discovery enhances understanding of electron transfer dynamics in complex molecular architectures.

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Published on: January 25, 2020

Area of Science:

  • Supramolecular Chemistry
  • Photochemistry
  • Materials Science

Background:

  • Developing advanced supramolecular systems for controlled electron transfer is crucial for energy applications.
  • Understanding charge-separated states and their stabilization is key to designing efficient molecular devices.

Purpose of the Study:

  • To develop a supramolecular oligochromophoric system with specific binding sites for electron acceptors and anions.
  • To investigate anion-binding-induced stabilization of the charge-separated state.

Main Methods:

  • Femtosecond and nanosecond laser flash photolysis to study intramolecular and intermolecular photochemical processes.
  • Investigating transient absorption spectra of supramolecular complexes.
  • Analyzing the effect of various anionic species on electron transfer and charge-separated state lifetimes.

Main Results:

  • Efficient electron transfer from porphyrin to fullerene moieties was observed, followed by rapid back electron transfer.
  • Anion binding at pyrrole amine groups enhanced photoinduced electron transfer rates.
  • Anion binding significantly prolonged the charge-separated state lifetime, with fluoride binding extending it 90-fold (163 ns to 14 μs).
  • Anion complexation lowered the oxoporphyrinogen oxidation potential, creating an intermediate state for charge migration.

Conclusions:

  • Anion binding effectively stabilizes the charge-separated state in the developed supramolecular system.
  • The stabilization is attributed to reduced oxidation potential and increased reorganization energy, decreasing charge recombination driving force.
  • This work demonstrates a strategy for controlling charge-separated state persistence through specific anion complexation.