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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals01:17

Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals

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Ideally, an unpaired electron shows a single peak in the EPR spectrum due to the transition between the two spin energy states. However, coupling interactions can occur between the spins of the unpaired electron and any neighboring spin-active nuclei. This hyperfine coupling results in hyperfine splitting, where the EPR signal is split into multiplets. The signals split into 2nI + 1 peaks, where n is the number of equivalent nuclei and I is the nuclear spin. These splitting patterns provide...
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Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

1.8K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
1.8K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.0K
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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Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
1.9K
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

1.9K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
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Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
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A Dynamic Metal-Organic Radical Emission System.

Xiang Li1, Yuan Wang2, Glib V Baryshnikov3,4

  • 1State Key Laboratory for Modification of Chemical Fiber and Polymer Materials, Key Lab of Science and Technology of Eco-Textile, Ministry of Education, College of Chemistry and Chemical Engineering, Donghua University, Shanghai, 201620, China.

Angewandte Chemie (International Ed. in English)
|December 23, 2024
PubMed
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Researchers developed novel dynamic radical luminescence systems using metal salts and carbonyl compounds. These systems exhibit tunable multi-band emission and can be used for sensing and information encryption.

Keywords:
dynamic luminescenceinformation encryptionmetal-organic radicalmulti-band emissionsupramolecular interactions

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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
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Area of Science:

  • Materials Science
  • Photochemistry
  • Supramolecular Chemistry

Background:

  • Developing organic radical emission systems with tunable luminescence is challenging.
  • Controlling emission properties requires novel molecular designs and assembly strategies.

Purpose of the Study:

  • To create dynamic, multi-emission band radical luminescence systems.
  • To regulate luminescence properties through co-assembly of metal salts and carbonyl compounds.

Main Methods:

  • Co-assembly of inorganic metal salts with carbonyl compounds in ionic liquids.
  • Characterization of luminescence properties under UV irradiation.
  • Investigation of ligand-metal charge transfer (LMCT) and ligand-metal-metal charge transfer (LMMCT) effects.

Main Results:

  • Achieved dual-band and excitation wavelength-dependent emission originating from carbonyl radicals and LMCT states.
  • Demonstrated three-band emission (visible to near-infrared) via LMMCT with co-doped metal ions.
  • Observed dynamic luminescence through visible-light-induced quenching of radical emission.
  • Enhanced photoluminescence quantum yield up to 67.2% due to LMMCT and supramolecular interactions.

Conclusions:

  • Developed a versatile platform for metal-organic radical emission systems.
  • Demonstrated potential applications in radioactive metal ion detection and information encryption.
  • Highlighted the role of LMCT and LMMCT in tuning luminescence properties.