RESUMEN
To enhance the efficiency of catalysis, it is crucial to comprehend the behavior of individual nanowires/nanosheets. A developed on-chip microcell facilitates this study by creating a reaction window that exposes the catalyst region of interest. However, this technology's potential application is limited due to frequently-observed variations in data between different cells. In this study, we identify a conductance problem in the reaction windows of non-metallic catalysts as the cause of this issue. We investigate this problem using in-situ electronic/electrochemical measurements and atom-thin nanosheets as model catalysts. Our findings show that a full-open window, which exposes the entire catalyst channel, allows for efficient modulation of conductance, which is ten times higher than a half-open window. This often-overlooked factor has the potential to significantly improve the conductivity of non-metallic catalysts during the reaction process. After examining tens of cells, we develop a vertical microcell strategy to eliminate the conductance issue and enhance measurement reproducibility. Our study offers guidelines for conducting reliable microcell measurements on non-metallic single nanowire/nanosheet catalysts.
RESUMEN
Sulfonyl and sulfonimidoyl fluorides are versatile substrates in organic synthesis and medicinal chemistry. However, they have been exclusively used as S(VI)+ electrophiles for defluorinative ligations. Converting sulfonyl and sulfonimidoyl fluorides to S(VI) radicals is challenging and underexplored due to the strong bond dissociation energy of SVI-F and high reduction potentials, but once achieved would enable dramatically expanded synthetic utility and downstream applications. In this report, we disclose a general platform to address this issue through cooperative organosuperbase activation and photoredox catalysis. Vinyl sulfones and sulfoximines are obtained with excellent E selectivity under mild conditions by coupling reactions with alkenes. The synthetic utility of this method in the preparation of functional polymers and dyes is also demonstrated.
