The practice of reaction window in an electrocatalytic on-chip microcell.

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.

Turning sulfonyl and sulfonimidoyl fluoride electrophiles into sulfur(VI) radicals for alkene ligation.

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.