Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 5, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202103559
Keywords
conformation; ensemble analysis; halogen bond; NAMFIS; NMR spectroscopy; RDC
Categories
Funding
- Swedish Research council [2020-03431, 2018-05973, 2021/5-359, 2021/22-350, 2020/5-435]
- Department of Chemistry - BMC
- Disciplinary Domain of Medicine and Pharmacy
- Swedish Research Council [2020-03431] Funding Source: Swedish Research Council
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This study introduces a strategy for accurate experimental description of weak chemical forces in solution, demonstrating its scope and effectiveness through experiments. The methodology utilizes entropic advantage and ensemble analysis to describe the orientation of weak force interactions, and derives thermodynamic constants through temperature-dependent chemical shift analysis.
Detection and characterisation of very weak, non-covalent interactions in solution is inherently challenging. Low affinity, short complex lifetime and a constant battle against entropy brings even the most sensitive spectroscopic methods to their knees. Herein we introduce a strategy for the accurate experimental description of weak chemical forces in solution. Its scope is demonstrated by the detailed geometric and thermodynamic characterisation of the weak halogen bond of a non-fluorinated aryl iodide and an ether oxygen (0.6 kJ mol(-1)). Our approach makes use of the entropic advantage of studying a weak force intramolecularly, embedded into a cooperatively folding system, and of the combined use of NOE- and RDC-based ensemble analyses to accurately describe the orientation of the donor and acceptor sites. Thermodynamic constants (Delta G, Delta H and Delta S), describing the specific interaction, were derived from variable temperature chemical shift analysis. We present a methodology for the experimental investigation of remarkably weak halogen bonds and other related weak forces in solution, paving the way for their improved understanding and strategic use in chemistry and biology.
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