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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 species into...
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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...
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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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Updated: Jan 11, 2026

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Revolutionary "Clip-Off" Strategy for Macrocycles from Covalent Organic Frameworks.

Xiang-Chun Li1, Weijie Yang1, Wen-Yong Lai1

  • 1State Key Laboratory of Flexible Electronics (LoFE), Institute of Advanced Materials (IAM), School of Chemistry and Life Sciences, Nanjing University of Posts & Telecommunications, Nanjing 210023, China.

Research (Washington, D.C.)
|November 10, 2025
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Summary

Researchers developed a novel "clip-off" strategy using covalent organic frameworks to efficiently synthesize large organic macrocycles. This method overcomes previous limitations, achieving high yields and simplifying purification for complex molecular structures.

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Area of Science:

  • Organic Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Traditional synthesis of complex organic macrocycles faces challenges like low yields and difficult purification.
  • Stepwise synthesis approaches often limit the size and structural complexity of achievable macrocycles.

Purpose of the Study:

  • To introduce a new strategy for the efficient synthesis of large and rigid organic macrocycles.
  • To overcome the limitations of conventional stepwise synthesis methods.

Main Methods:

  • Utilized designed covalent organic frameworks (COFs) with incorporated cleavable bonds.
  • Employed a precise ozonolysis technique to release macrocycles from the COF pores.
  • Leveraged reticular chemistry principles to control macrocycle size and functionality.

Main Results:

  • Achieved near-quantitative yields of macrocycles with ring sizes from 114 to 162 atoms.
  • Demonstrated a significant improvement in efficiency and selectivity compared to stepwise methods.
  • Established crystalline frameworks as effective molecular blueprints for macrocycle synthesis.

Conclusions:

  • The "clip-off" strategy offers a transformative approach to macrocycle synthesis.
  • Covalent organic frameworks can serve as templates for controlled synthesis of complex molecular architectures.
  • This method significantly advances the field of macrocyclic chemistry and materials science.