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Related Concept Videos

Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

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.
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

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.
Selection Rules: Photochemical Activation
Photosystem I01:27

Photosystem I

Although structurally similar to photosystem II (PSII), photosystem I (PSI) is has a different electron supplier and electron acceptor.
Both these photosystems work in concert. An excited electron from PSII is relayed to PSI via an electron transport chain in the thylakoid membrane of the chloroplast, which is comprised of the carrier molecule plastoquinone, the dual-protein cytochrome complex, and plastocyanin. As electrons move between PSII and PSI, they lose energy and must be re-energized...
The Z-Scheme of Electron Transport in Photosynthesis01:34

The Z-Scheme of Electron Transport in Photosynthesis

The light reactions of photosynthesis assume a linear flow of electrons from water to NADP+. During this process, light energy drives the splitting of water molecules to produce oxygen. However, oxidation of water molecules is a thermodynamically unfavorable reaction and requires a strong oxidizing agent. This is accomplished by the first product of light reactions: oxidized P680 (or P680+), the most powerful oxidizing agent known in biology. The oxidized P680 that acquires an electron from the...
Photosystem II01:22

Photosystem II

The multi-protein complex photosystem II (PS II) harvests photons and transfers their energy through its bound pigments to its reaction center, and ultimately to photosystem I (PSI) through the electron transport chain. The pigments responsible for caputirng the light energy in photosystems include chlorophyll a, chlorophyll b, and carotenoids.
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The Photochemical Reaction Center01:29

The Photochemical Reaction Center

Reaction centers are pigment-protein complexes that initiate energy conversion from photons to chemical entities. Therefore, photochemical reaction center is a more appropriate term that describes these complexes. The Nobel laureates Robert Emerson and William Arnold provided the first experimental evidence of photochemical reaction centers by demonstrating the participation of nearly 2,500 chlorophyll molecules for the release of just one molecule of oxygen. Despite thousands of photosynthetic...

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Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions
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Visible-Light-Induced Hydrosilylation Enabled by an In Situ Assembled Photoactive Complex.

Siqing Liu1, Wanhui Huang1, Denghui Ma2

  • 1State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou 350002, China.

Organic Letters
|July 10, 2026
PubMed
Summary

This study introduces a novel photosensitizer-free method for visible-light-driven hydrosilylation. The process generates silicon-centered radicals from tris(trimethylsilyl)silane, enabling alkene and alkyne hydrosilylation and dehalogenation without external catalysts.

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Area of Science:

  • Organic Chemistry
  • Photochemistry
  • Radical Chemistry

Background:

  • Traditional hydrosilylation often requires expensive or toxic photocatalysts and initiators.
  • Visible-light photoredox catalysis has emerged as a powerful tool in organic synthesis.
  • Developing catalyst-free or initiator-free visible-light-driven reactions is highly desirable for sustainable chemistry.

Purpose of the Study:

  • To develop a photosensitizer-free, visible-light-driven protocol for hydrosilylation.
  • To generate silicon-centered radicals in situ for synthetic applications.
  • To explore the utility of these radicals in both hydrosilylation and dehalogenation reactions.

Main Methods:

  • Mixing tris(trimethylsilyl)silane with cesium carbonate (Cs2CO3) to form a visible-light-absorbing species.
  • Irradiation of the mixture at 456 nm to generate silicon-centered radicals.
  • Reaction of the generated radicals with various alkenes and alkynes for hydrosilylation, and with halogenated compounds for dehalogenation.

Main Results:

  • Successful generation of silicon-centered radicals upon visible-light irradiation without any exogenous photocatalyst.
  • Efficient hydrosilylation of a diverse range of alkenes and alkynes using the generated radicals.
  • Demonstration of the radicals' ability to act as halogen-atom transfer reagents for dehalogenation reactions.
  • Elimination of the need for external initiators, photocatalysts, or HAT mediators.

Conclusions:

  • A novel and efficient photosensitizer-free, visible-light-driven hydrosilylation reaction has been established.
  • The developed method provides a sustainable alternative for silicon-centered radical generation and utilization.
  • This strategy offers a simplified and more environmentally friendly approach to hydrosilylation and dehalogenation.