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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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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

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All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
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meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H01:13

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All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...
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Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
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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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Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
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Lanthanide chains containing the naphthalenyl nitronyl nitroxide radical.

Charlie V Sarmiento1, Thamyres A Araujo2, Samira G Reis2

  • 1Instituto de Física, Universidade Federal Do Rio de Janeiro Rio de Janeiro RJ Brazil.

RSC Advances
|May 9, 2022
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Summary

Researchers synthesized lanthanide-based one-dimensional compounds, [Lanthanide(hfac)3(NaphNN)], revealing helical chains and significant magnetic interactions. Dynamic magnetic properties suggest single-chain magnet behavior in Dy and Tb compounds.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Magnetism

Background:

  • Lanthanide ions are crucial in developing single-molecule magnets.
  • One-dimensional coordination polymers offer unique magnetic properties.
  • Nitronyl nitroxide radicals are effective magnetic building blocks.

Purpose of the Study:

  • Synthesize and characterize novel lanthanide-based one-dimensional compounds.
  • Investigate the magnetic properties and interactions within these chains.
  • Explore the potential for single-chain magnet behavior.

Main Methods:

  • Single crystal X-ray diffraction for structural analysis.
  • Magnetic susceptibility measurements (temperature and frequency dependence).
  • Fitting magnetic data using a six-membered ring model.

Main Results:

  • Successful synthesis of [Ln(hfac)3(NaphNN)] compounds (Ln = Gd, Dy, Tb).
  • Crystal structure reveals isolated twofold helical chains.
  • Significant intrachain interactions (Gd-NN, Gd-Gd, NN-NN) observed.
  • Antiferromagnetic coupling between nitronyl nitroxide radicals confirmed.
  • Evidence of single-chain magnet dynamics in Dy and Tb compounds.

Conclusions:

  • The synthesized lanthanide compounds exhibit complex magnetic interactions.
  • Helical chain structures influence magnetic behavior.
  • Dynamic magnetic properties indicate potential for single-chain magnet applications.