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Abstract Electrochemistry represents unique approaches for the promotion and mechanistic study of chemical reactions and has garnered increasing attention in different areas of chemistry. This expansion necessitates the enhancement of the traditional electrochemical cells that are intrinsically constrained by mass transport limitations. Herein, we present an approach for designing an electrochemical cell by limiting the reaction chamber to a thin layer of solution, comparable to the thickness of the diffusion layer. This thin layer electrode (TLE) provides a modular platform to bypass the constraints of traditional electrolysis cells and perform electrolysis reactions in the timescale of electroanalytical techniques. The utility of the TLE for electrosynthetic applications benchmarked using NHPI‐mediated electrochemical C−H functionalization. The application of microscale electrolysis for the study of drug metabolites was showcased by elucidating the oxidation pathways of the paracetamol drug. Moreover, hosting a microelectrode in the TLE, was shown to enable real‐time probing of the profiles of redox‐active components of these rapid electrosynthesis reactions. 

Abstract New stimulus‐responsive scaffolds are of interest as constituents of hierarchical supramolecular ensembles. 1,3,5–2,4,6‐Functionalized, facially segregated benzene moieties have a time‐honored role as building blocks for host molecules. However, their user as switchable motifs in the construction of multi‐component supramolecular structures remains poorly explored. Here, we report a molecular cage 1, which consists of a bent anthracene dimer3paired with 1,3,5‐tris(aminomethyl)‐2,4,6‐triethylbenzene2. As the result of the pH‐inducedababab↔bababaisomerization of the constituent‐functionalized benzene units derived from2, this cage can reversibly convert between an open state and a closed form, both in solution and in the solid state. Cage 1was used to create stimuli‐responsive hierarchical superstructures, namely Russian doll‐like complexes with [K⊂18‐crown‐6⊂1]⁺and [K⊂cryptand‐222⊂1]⁺. The reversible assembly and disassembly of these superstructures could be induced by switching cage 1from its open to closed form. The present study thus provides an unusual example where pH‐triggered conformation motion within a cage‐like scaffold is used to control the formation and disassociation of hierarchical ensembles.