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Related Concept Videos

Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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 generated carbocation,...
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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 catalyst, high molecular...
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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 the...
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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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Novel lanthanide-based polymeric chains and corresponding ultrafast dynamics in solution.

Dominique T Thielemann1, Melanie Klinger, Thomas J A Wolf

  • 1Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Engesserstr. 15, 76131 Karlsruhe, Germany.

Inorganic Chemistry
|November 10, 2011
PubMed
Summary

New coordination polymers with lanthanide and alkali metals were synthesized. These materials show lanthanide-specific energy transfer dynamics and magnetic properties, with potential as single-molecule magnets.

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Published on: April 14, 2020

Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Spectroscopy

Background:

  • Lanthanide coordination polymers offer unique electronic and magnetic properties.
  • Dibenzoylmethane (Ph(2)acacH) is a versatile ligand for creating metal complexes.
  • Understanding energy transfer and magnetic relaxation in these materials is crucial for advanced applications.

Purpose of the Study:

  • To synthesize and characterize novel one-dimensional coordination polymers of lanthanides with dibenzoylmethane.
  • To investigate the dissociation behavior, photophysical properties, and magnetic characteristics of these polymers.
  • To explore the influence of lanthanide and alkali metal ions on material properties.

Main Methods:

  • Synthesis of coordination polymers using lanthanide trichloride hydrates, dibenzoylmethane, and alkali metal bases (Cs(2)CO(3) or KOtBu).
  • Characterization using electrospray ionization mass spectrometry (ESI-MS) and femtosecond laser spectroscopy.
  • Magnetic studies, including magnetization relaxation and hysteresis loop measurements.

Main Results:

  • Successful synthesis of two types of heterobimetallic coordination polymers: [Cs{Ln(Ph(2)acac)(4)}](n) and [K{Nd(Ph(2)acac)(4)}](n).
  • Dissociation of all synthesized compounds in DMF solutions observed via ESI-MS.
  • Lanthanide-specific relaxation dynamics observed with relaxation times from picoseconds to hundreds of picoseconds, indicating intramolecular energy transfer.
  • The dysprosium-containing polymer, [Cs{Dy(Ph(2)acac)(4)}](n), exhibits single-ion single molecule magnet (SMM) behavior and weak single chain magnet (SCM) behavior.

Conclusions:

  • The synthesized coordination polymers exhibit complex dissociation behavior in solution.
  • Intramolecular energy transfer from ligands to lanthanides is a key photophysical process, dependent on the specific lanthanide ion.
  • The dysprosium-based polymer demonstrates promising single-molecule magnet properties, paving the way for future magnetic materials research.