Halogen Bonding in Dithiane/Iodofluorobenzene Mixtures: A New Class of Hydrophobic Deep Eutectic Solvents.
Halogen Bonding in Dithiane/Iodofluorobenzene Mixtures: A New Class of Hydrophobic Deep Eutectic Solvents.
复制标题
二噻烷/碘氟苯混合物中的卤素键合：一类新型疏水性低共熔溶剂。
DOI：
10.1002/anie.202110520
复制
发表时间：
2021
影响因子：
--
通讯作者：
W. Pennington
中科院分区：
文献类型：
--
作者：
Andrew J. Peloquin;Jena M. McCollum;C. McMillen;W. Pennington
虽然对深共熔溶剂（DES）的研究在过去的二十年中有所扩展，但重点仍然是在这些系统中利用氢键供体。此外，大多数已知的DES依赖于至少一种离子组分。通过1，3-二噻烷和1，2-二碘-3，4，5，6-四氟苯（1，2-F_4DIB）的化合，首次报道了一种基于卤素键的DES。该混合物保持为液体，在1，3-二噻烷摩尔分数（0.35至0.75）的范围内具有13.7°C的共晶熔融温度。此外，通过单晶X射线衍射研究了1，3-和1，4-二噻烷与1，2-、1，3-和1，4-F4 DIB以及1，3，5-三氟-2，4，6-三碘苯的共晶。这些数据揭示了宽范围的卤素键合强度（0.85 < Rxb < 0.99; Rxb =归一化卤素键距离参数）和关于硫原子的几何形状。通过包括氢键之外的分子间相互作用，可以大大扩展可能的DES系统的范围。
While research into deep eutectic solvents (DESs) has expanded over the previous two decades, the focus has remained on the utilization of hydrogen bond donors in these systems. Additionally, the majority of the known DESs rely on at least one ionic component. Through the combination of 1,3-dithiane and 1,2-diiodo-3,4,5,6-tetrafluorobenzene (1,2-F4DIB), we report the first known DES based on halogen bonding. This mixture remains a liquid, with a eutectic melting temperature of 13.7°C over a range of 1,3-dithiane mole fraction (0.35 to 0.75). Additionally, cocrystals of 1,3- and 1,4-dithiane with 1,2-, 1,3-, and 1,4-F4DIB, as well as 1,3,5-trifluoro-2,4,6-triiodobenzene were studied via single-crystal X-ray diffraction. These data reveal a wide range of halogen bonding strengths (0.85 < RXB < 0.99; Rxb = normalized halogen bond distance parameter) and geometries about the sulfur atom. By including intermolecular interactions beyond hydrogen bonding, the scope of possible DES systems can be greatly expanded.