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Related Concept Videos

Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
Pericyclic Reactions: Introduction01:17

Pericyclic Reactions: Introduction

Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...
Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...

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Related Experiment Video

Updated: May 19, 2026

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
09:12

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

Photoredox catalysis for polymerization reactions.

Jacques Lalevée1, Mohamad-Ali Tehfe, Fabrice Morlet-Savary

  • 1Institut de Science des Matériaux de Mulhouse IS2M - LRC CNRS 7228 - ENSCMu-UHA 15, rue Jean Starcky, 68057 Mulhouse Cedex, France. j.lalevee@uha.fr

Chimia
|August 9, 2012
PubMed
Summary

Photoredox catalysis enables free radical generation under mild conditions, now applied to polymer chemistry. This review details photocatalyst advancements in ring-opening and free radical polymerizations.

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Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Published on: November 21, 2017

Area of Science:

  • Polymer Chemistry
  • Photoredox Catalysis
  • Organic Synthesis

Background:

  • Photoredox catalysis is established for generating free radicals in organic synthesis.
  • It operates under mild irradiation conditions, including sunlight and LED lighting.
  • This technique has potential applications in polymer chemistry.

Purpose of the Study:

  • To introduce photoredox catalysis to polymer chemistry.
  • To review the current achievements of photocatalysts in initiating polymerizations.
  • To focus on ring-opening polymerization (ROP) and free radical polymerization (FRP).

Main Methods:

  • Application of photoredox catalysis principles to polymer synthesis.
  • Initiation of ring-opening polymerizations (ROP).
  • Initiation of free radical polymerizations (FRP).

Main Results:

  • Demonstration of photoredox catalysis for initiating both FRP and ROP.
  • Highlighting the effectiveness of photocatalysts under soft irradiation.
  • Providing an updated overview of photocatalyst performance in these polymerization types.

Conclusions:

  • Photoredox catalysis is a viable and efficient method for initiating polymerizations.
  • The technique offers advantages due to mild reaction conditions.
  • This review summarizes key advancements in photocatalyst applications for FRP and ROP.