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Updated: Jul 11, 2025

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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双发射矩形超分子 Pt(II) -p-双与4,4'-双二衍生物金属循环:逐步合成和光物理特性

Antonia Garypidou1, Konstantinos Ypsilantis1, John C Plakatouras1,2

  • 1Department of Chemistry, University of Ioannina, GR-45110 Ioannina, Greece.

Molecules (Basel, Switzerland)
|November 14, 2023
PubMed
概括

新的 (II) 超分子协调复合物 (SCCs) 被合成和表征. 它们的排放特性取决于桥接联体长度和溶剂极性,其中一些由于聚合诱导的排放而表现出双排放.

关键词:
聚合引发的排放量 聚合引发的排放量金 (二) 金 (二)一步一步的合成.在超分子协调复合体中.

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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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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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The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
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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.
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