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Step-Growth Polymerization: Overview01:03

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Olefin Metathesis Polymerization: Overview01:13

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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.
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A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
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Updated: Jan 16, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Driving Multi-Step Regioselectivity in On-Surface Polymer Synthesis by Molecular Coverage.

Kalyan Biswas1, Alba García-Frutos1, Berta Álvarez2

  • 1IMDEA Nanoscience, Campus de Cantoblanco, C/ Faraday 9, Madrid, 28049, Spain.

Angewandte Chemie (International Ed. in English)
|October 6, 2025
PubMed
Summary
This summary is machine-generated.

Researchers achieved regioselective polymerization on gold surfaces by controlling molecular coverage. This method allows precise tuning of polymer structure and dimensionality for advanced nanomaterials.

Keywords:
On‐surface synthesisPolymer scienceRegioselectivityScanning probe microscopy

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Area of Science:

  • Surface Science
  • Polymer Chemistry
  • Nanomaterials Synthesis

Background:

  • On-surface synthesis enables precise design of organic nanomaterials.
  • Regioselective control in polymerization is crucial for tailoring material properties.

Purpose of the Study:

  • To demonstrate a novel approach for regioselective polymerization on Au(111).
  • To investigate the influence of molecular coverage on polymerization outcomes.

Main Methods:

  • Utilized scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM).
  • Employed density functional theory (DFT) calculations.
  • Synthesized polymers from a dicyclopentaanthracene precursor on Au(111).

Main Results:

  • Observed a molecular coverage-dependent regioselective homocoupling mechanism.
  • Low coverage yielded 1D polymers via anti-configuration indenyl couplings.
  • Half monolayer coverage resulted in quasi-1D staircase polymers.
  • Higher coverages led to 2D porous networks driven by benzylic position activation.

Conclusions:

  • Molecular coverage is a key factor in steering regioselectivity and polymer dimensionality.
  • This work advances on-surface synthesis and polymer science by enabling controlled polymerization.