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Related Concept Videos

Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

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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.
Along with electronic...
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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Stabilizing Radicals in Aggregation-Induced Emission Rotor-Polyoxometalate Crystals for Efficient Photothermal

Guokang He1, Xinwen Ou1, Cheng Liu1

  • 1Department of Chemistry, and the Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR 999077, China.

Journal of the American Chemical Society
|February 28, 2026
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Researchers developed a novel crystalline photothermal material, APC, using polyoxometalate clusters and aggregation-induced emission rotors. This material efficiently converts solar energy to heat, achieving 88.7% efficiency and enabling 97.5% solar-to-vapor water evaporation.

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Area of Science:

  • Materials Science
  • Renewable Energy
  • Nanotechnology

Background:

  • Developing efficient photothermal materials is key for renewable energy, especially for near-infrared solar spectrum utilization.
  • Current materials often sacrifice structural precision for performance, hindering advancements in solar energy conversion.
  • Achieving broadband absorption, high efficiency, and precise crystalline structure simultaneously is a significant challenge.

Purpose of the Study:

  • To report a novel crystalline photothermal material synthesized via a one-pot method.
  • To demonstrate the first use of aggregation-induced emission (AIE) rotor-polyoxometalate (POM) assemblies for photothermal conversion.
  • To elucidate the mechanism of radical generation and stabilization for enhanced photothermal properties.

Main Methods:

  • One-pot synthesis of the APC material by assembling POM clusters with amino-modified tetraphenylethylene (AIE rotor).
  • Utilizing trace peroxides in solvents to oxidize AIE rotors, initiating radical formation stabilized by the crystalline matrix.
  • Investigating charge transfer mechanisms between AIE rotors and POMs using mechanistic studies.

Main Results:

  • The synthesized APC material exhibits broadband absorption beyond 2000 nm due to air-stable radicals.
  • Achieved an exceptional photothermal conversion efficiency of 88.7% under 808 nm laser irradiation.
  • Demonstrated a high solar-to-vapor water evaporation efficiency of 97.5% under 1 sun illumination.

Conclusions:

  • Introduced a rational design strategy for crystalline photothermal hybrid materials.
  • Established mechanistic links between molecular assembly, charge transfer, and radical stabilization in photothermal conversion.
  • The APC material shows significant promise for applications in solar-driven desalination and renewable energy technologies.