Tuning Supramolecular Selectivity for Hydrosulfide: Linear Free Energy Relationships Reveal Preferential C-H Hydrogen Bond Interactions.

Autor:	Fargher HA; Department of Chemistry & Biochemistry, Materials Science Institute, and Knight Campus for Accelerating Scientific Impact, University of Oregon, Eugene, Oregon 97403-1253, United States., Lau N; Department of Chemistry & Biochemistry, Materials Science Institute, and Knight Campus for Accelerating Scientific Impact, University of Oregon, Eugene, Oregon 97403-1253, United States., Richardson HC; Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331, United States., Cheong PH; Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331, United States., Haley MM; Department of Chemistry & Biochemistry, Materials Science Institute, and Knight Campus for Accelerating Scientific Impact, University of Oregon, Eugene, Oregon 97403-1253, United States., Pluth MD; Department of Chemistry & Biochemistry, Materials Science Institute, and Knight Campus for Accelerating Scientific Impact, University of Oregon, Eugene, Oregon 97403-1253, United States., Johnson DW; Department of Chemistry & Biochemistry, Materials Science Institute, and Knight Campus for Accelerating Scientific Impact, University of Oregon, Eugene, Oregon 97403-1253, United States.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2020 May 06; Vol. 142 (18), pp. 8243-8251. Date of Electronic Publication: 2020 Apr 24.
DOI:	10.1021/jacs.0c00441
Abstrakt:	Supramolecular anion receptors can be used to study the molecular recognition properties of the reactive yet biologically critical hydrochalcogenide anions (HCh - ). Achieving selectivity for HCh - over the halides is challenging but necessary for not only developing future supramolecular probes for HCh - binding and detection, but also for understanding the fundamental properties that govern these binding and recognition events. Here we demonstrate that linear free energy relationships (LFERs)-including Hammett and Swain-Lupton plots-reveal a clear difference in sensitivity to the polarity of an aryl C-H hydrogen bond (HB) donor for HS - over other HCh - and halides. Analysis using electrostatic potential maps highlights that this difference in sensitivity results from a preference of the aryl C-H HB donor for HS - in this host scaffold. From this study, we demonstrate that LFERs are a powerful tool to gain interpretative insight into motif design for future anion-selective supramolecular receptors and highlight the importance of C-H HB donors for HS - recognition. From our results, we suggest that aryl C-H HB donors should be investigated in the next generation of HS - selective receptors based on the enhanced HS - selectivity over other competing anions in this system.
Databáze:	MEDLINE
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