Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
Department of Chemistry and Biochemistry, University of California, San Diego, California 92093, United States.
J Org Chem. 2021 Jun 18;86(12):8425-8436. doi: 10.1021/acs.joc.1c00921. Epub 2021 Jun 2.
A systematic study of arene-perfluoroarene interactions in solution is presented. Using a combination of NMR titration experiments, X-ray crystallography, and computational analysis, we analyze the effects of fluorination, substituents, ring size, and solvation on the arene-perfluoroarene interaction. We find that fluorination, extension of the π systems, and enhancement of solvent polarity greatly stabilize the stacking energy up to 3 orders of magnitude ( = <1 to 6000 M), with the highest achieved for the interaction of water-soluble variants of perfluoronaphthalene and anthracene in buffered DO (pD = 12). Combining computational and experimental results, we conclude that this impressive binding energy is a result of enthalpically favorable electrostatic and dispersion interactions as well as the entropically driven hydrophobic effect. The enhanced understanding of arene-perfluoroarene interactions in aqueous solution sets the stage for the implementation of this abiotic intermolecular interaction in biology and medicine.
本文系统研究了溶液中芳烃-全氟芳烃相互作用。通过 NMR 滴定实验、X 射线晶体学和计算分析相结合，我们分析了氟取代、取代基、环大小和溶剂化对芳烃-全氟芳烃相互作用的影响。我们发现，氟化、π 体系的扩展和溶剂极性的增强极大地稳定了堆积能，高达 3 个数量级（ = <1 至 6000 M），其中水溶性全氟萘和蒽变体在缓冲 DO（pD = 12）中的相互作用达到最高值。结合计算和实验结果，我们得出结论，这种令人印象深刻的结合能是由于焓有利的静电和色散相互作用以及熵驱动的疏水作用的结果。对水溶液中芳烃-全氟芳烃相互作用的深入了解为在生物学和医学中实施这种非生物分子间相互作用奠定了基础。
