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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.
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In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
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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: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

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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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Radical Reactivity: Overview01:11

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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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Color in Coordination Complexes
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Stable Radical Iridium(III) Complexes with Tunable Panchromatic Absorption.

Sergei V Tatarin1, Ivan Zhuravlev1,2, Maxim M Minin1,2

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Researchers developed stable, panchromatic iridium complexes with tunable light absorption up to the infrared region. These redox-active metalloradicals show promise for solar cells and photothermal therapy.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Photochemistry

Background:

  • Designing stable, panchromatic metal complexes with reversible redox behavior is challenging.
  • New ligand platforms are needed to broaden the absorption spectrum of metal complexes.

Purpose of the Study:

  • Synthesize and characterize novel octahedral bis-cyclometalated iridium(III) complexes.
  • Investigate their stability, absorption properties, redox behavior, and potential applications.

Main Methods:

  • Synthesis of iridium(III) complexes featuring redox-active ancillary ligands (o-semiquinone/o-iminosemiquinone).
  • Characterization using spectroscopic and electrochemical techniques.
  • Evaluation in dye-sensitized solar cells (TiO2 photoanodes) and photothermal conversion studies.

Main Results:

  • Achieved exceptional chemical stability and intense panchromatic absorption up to ~1050 nm.
  • Demonstrated independently tunable absorption maxima in UV-vis and vis-NIR regions.
  • Observed predominantly reversible electrochemical behavior and efficient photothermal conversion under IR irradiation.

Conclusions:

  • Developed a strategy for stable, tunable, panchromatic metalloradicals.
  • Showcased potential applications in dye-sensitized solar cells and photothermal therapy.
  • Highlighted the versatility of ancillary ligand design for controlling iridium species and functionality.