English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Herein, we examine the photochemical formation of reactive oxygen species (ROS) by a porous benzophenone-containing bis-urea host ( 1 ) to investigate the mechanism of photooxidations that occur within the confines of its nanochannels. UV irradiation of the self-assembled host in the presence of molecular oxygen generates both singlet oxygen and superoxide when suspended in solution. The efficiency of ROS generation by the host is lower than that of benzophenone (BP), which could be beneficial for reactions carried out catalytically, as ROS species react quickly and often unselectively. Superoxide formation was detected through reaction with 5,5-dimethyl-1-pyrroline N -oxide in the presence of methanol. However, it is not detected in CHCl 3 , as it reacts rapidly with the solvent to generate methaneperoxy and chloride anions, similar to BP. The lifetime of airborne singlet oxygen (τ Δairborne ) was examined at the air-solid outer surface of the host and host·quencher complexes and suggests that quenching is a surface phenomenon. The efficiency of the host and BP as catalysts was compared for the photooxidation of 1-methyl-1-cyclohexene in solution. Both the host and BP mediate the photooxidation in CHCl 3 , benzene, and benzene- d  6 , producing primarily epoxide-derived products with low selectivity likely by both type I and type II photooxidation processes. Interestingly, in CHCl 3 , two chlorohydrins were also formed, reflecting the formation of chloride in this solvent. In contrast, UV irradiation of the host·guest crystals in an oxygen atmosphere produced no epoxide and appeared to favor mainly the type II processes. Photolysis afforded high conversion to only three products: an enone, a tertiary allylic alcohol, and a diol, which demonstrates the accessibility of the encapsulated reactants to oxygen and the influence of confinement on the reaction pathway.

Probing the Formation of Reactive Oxygen Species by a Porous Self-Assembled Benzophenone Bis-Urea Host