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Related Concept Videos

Redox Reactions01:24

Redox Reactions

Oxidation-reduction or redox reactions involve the transfer of electrons from one molecule or atom to another. When an atom gains an electron, another atom must lose an electron, meaning oxidation and reduction must occur together. Since the redox occurs in pairs, the atom that gets oxidized is also called the reducing agent or reductant, and the atom that is reduced is also called the oxidizing agent or oxidant. A straightforward way to remember the definitions of oxidation and reduction is...
Redox Reactions01:27

Redox Reactions

Redox reactions are vital biochemical processes that underpin energy metabolism in cells. These reactions involve the transfer of electrons between molecules, occurring in tandem as oxidation and reduction. Oxidation refers to the loss of electrons, while reduction denotes their gain. This coupling ensures the seamless flow of electrons through metabolic pathways. For example, in bacterial metabolism, glucose undergoes oxidation to carbon dioxide, while oxygen is simultaneously reduced to...
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired molecule. These three...
Resonance and Hybrid Structures02:16

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According to the theory of resonance, if two or more Lewis structures with the same arrangement of atoms can be written for a molecule, ion, or radical, the actual distribution of electrons is an average of that shown by the various Lewis structures.
Resonance Structures and Resonance Hybrids
The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N–O and N=O bonds.
Redox Equilibria: Overview01:23

Redox Equilibria: Overview

A reduction-oxidation reaction is commonly called a redox reaction. In a redox reaction, electrons are transferred from one species to another rather than being shared between or among atoms. The reducing agent or reductant is the species that loses electrons and gets oxidized in the process. The species that gains electrons and gets reduced in the process is the oxidizing agent or oxidant. Redox reactions are represented as two separate equations called half-reactions, where one equation...
Molecular Models02:00

Molecular Models

Physical models representing molecular architectures of chemical compounds play essential roles in understanding chemistry. The use of molecular models makes it easier to visualize the structures and shapes of atoms and molecules.

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Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals
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Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals

Published on: May 29, 2018

Redox-responsive molecular helices with highly condensed π-clouds.

Eisuke Ohta1, Hiroyasu Sato, Shinji Ando

  • 1RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.

Nature Chemistry
|December 17, 2010
PubMed
Summary

This study reveals a redox-responsive helical oligomer that exhibits dynamic motion and chiral symmetry-breaking during crystallization. Oxidation locks the helix, creating a lasting chiroptical memory.

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Area of Science:

  • Organic Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Helical structures are crucial in chemistry for chiral applications like compound separation and molecular machines.
  • Polymeric ortho-phenylenes naturally form tight helices due to steric forces, creating dense pi-clouds.

Purpose of the Study:

  • To investigate the dynamic motion and redox-responsive behavior of an oligomeric ortho-phenylene.
  • To explore the phenomenon of chiral symmetry-breaking during crystallization in helical systems.
  • To understand the mechanism of conformational locking induced by oxidation.

Main Methods:

  • Synthesis and characterization of a helical oligomeric ortho-phenylene.
  • Solution-state dynamic motion analysis (inversion rates).
  • X-ray crystallography of both neutral and oxidized forms.
  • Spectroscopic analysis to study the electronic changes upon oxidation.

Main Results:

  • The helical oligomer exhibits rapid inversion in solution.
  • Crystallization leads to chiral symmetry-breaking, yielding enantiomerically enriched crystals.
  • One-electron oxidation significantly suppresses the dynamic helical motion.
  • X-ray crystallography reveals a delocalized hole in the oxidized form, causing conformational locking.

Conclusions:

  • The redox-responsive helical oligomer demonstrates tunable dynamics and controllable chirality.
  • Oxidation-induced conformational locking provides a mechanism for long-lasting chiroptical memory.
  • This work opens avenues for designing dynamic chiral materials and molecular switches.