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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.1K
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...
2.1K
Radical Formation: Overview01:03

Radical Formation: Overview

2.1K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

2.6K
The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this...
2.6K
Radical Formation: Addition00:47

Radical Formation: Addition

1.7K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
1.7K
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
1.8K
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

2.0K
The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
2.0K

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Radical-pairing-induced molecular assembly and motion.

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  • 1Department of Chemistry, Nankai University, Tianjin, China. kangcai@nankai.edu.cn.

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Conjugated organic π-radicals enable novel molecular recognition through radical-pairing interactions. This facilitates advancements in supramolecular assembly, molecular machines, and stimuli-responsive materials science.

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science
  • Organic Chemistry

Background:

  • Radical-pairing interactions involving conjugated organic π-radicals are emerging motifs in supramolecular chemistry.
  • These interactions offer unique electronic, magnetic, optical, and redox-responsive properties.
  • Conjugated π-radicals are key components in advanced molecular designs.

Purpose of the Study:

  • To review radical-pairing based recognition processes.
  • To highlight applications in supramolecular assembly and mechanically interlocked molecules.
  • To explore use in stimuli-controlled molecular switches and unidirectional molecular transporters.

Main Methods:

  • Overview of existing literature and examples of radical-pairing interactions.
  • Analysis of molecular designs incorporating radical-pairing for specific functions.
  • Discussion of redox stimulation for controlling assembly and motion.

Main Results:

  • Demonstration of radical-pairing interactions in directed supramolecular assembly.
  • Application in templating mechanically interlocked molecules.
  • Utilization in stimuli-responsive molecular switches and powered molecular transporters.

Conclusions:

  • Radical-pairing interactions are versatile tools in supramolecular chemistry and materials science.
  • Redox-switchable radical-pairing offers control over molecular assembly and motion.
  • Future directions include further development of molecular transporters and non-equilibrium systems.