The rarely recognized electron donating ability of the benzophenone triplet excited state provides an unusual route for the photochemical synthesis of gold nanoparticles.
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http://dx.doi.org/10.1039/c3pp50247c | DOI Listing |
J Am Chem Soc
December 2024
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Photochemical deracemization has emerged as one of the most straightforward approaches to access highly enantioenriched compounds in recent years. While excited-state events such as energy transfer, single electron transfer, and ligand-to-metal charge transfer have been leveraged to promote stereoablation, approaches relying on hydrogen atom transfer, which circumvent the limitations imposed by the triplet energy and redox potential of racemic substrates, remain underexplored. Conceptually, the most attractive method for tertiary stereocenter deracemization might be hydrogen atom abstraction followed by hydrogen atom donation.
View Article and Find Full Text PDFPhys Chem Chem Phys
November 2024
Institute of Nuclear Chemistry and Technology, Dorodna 16, Warsaw 03-195, Poland.
Early stages of radiolysis of solutions with 2,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4]triazin-3-yl)pyridine (CyMe4-BTP) and 6,6'-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo-[1,2,4-]triazin-3-yl)-[2,2']bipyridine (CyMe4-BTBP) ligands in cyclohexanone, proposed as a solvent for selective actinide extraction, were studied by means of the pulse radiolysis technique with spectrophotometric detection. Transient UV-vis spectra of excited triplet states of ligands, formed by energy transfer from cyclohexanone excited triplet states to ligands, were recorded for the first time. The influence of typical extraction conditions (the presence of diluted acid and O from air) on the mechanisms of reactions in the system studied was assessed.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
College of Chemistry and Chemical Engineering, Key (Guangdong-Hong Kong Joint) Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong, 515063, P. R. China.
J Org Chem
November 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, People's Republic of China.
We describe a metal-free and mild three-component reaction utilizing vinylarenes, alkyl aldehydes, and 4-cyanopyridine. In this reaction, the scope of vinylarenes and alkyl aldehydes includes over 40 examples, generating a variety of β-pyridinyl ketones. Moreover, potential applications of this method have been demonstrated by the functionalization of pharmaceutical molecules.
View Article and Find Full Text PDFJ Phys Chem A
September 2024
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, United States.
The photochemical decomposition of ethyl(aqua)cobaloxime, [EtCo(dmgH)HO], a vitamin B derivative model complex, was investigated to understand the mechanism of the Co-C bond scission induced by light. Upon irradiation of [EtCo(dmgH)HO], the Co-C bond undergoes homolytic scission, resulting in Et/Co(II) radical pair (RP) formation in a similar fashion observed in alkylcobalamins. The [EtCo(dmgH)HO] complex acts as a potent quencher of a wide variety of excited states in the presence of organic molecules such as benzophenone.
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