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在发光有机基中可逆旋光接口

  • 0Cavendish Laboratory, University of Cambridge, Cambridge, UK. sg911@cam.ac.uk.

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Radical Reactivity: Nucleophilic Radicals 01:16

2.1K

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...

Radical Reactivity: Overview 01:11

2.1K

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...

Radical Formation: Overview 01:03

2.1K

A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...

Radical Formation: Addition 00:47

1.7K

Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...

Photoluminescence: Fluorescence and Phosphorescence 01:23

2.1K

Photoluminescence is a process where a molecule absorbs light energy and re-emits it in the form of light. This phenomenon occurs when a substance absorbs photons, promoting its electrons to higher energy level excited states, followed by a relaxation process in which the electrons return to their original ground state energy levels and emit light. Photoluminescence is widely observed in various materials, including semiconductors, and organic and inorganic compounds.
A pair of electrons in a...

Photochemical Electrocyclic Reactions: Stereochemistry 01:26

1.9K

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