论文标题

二甲基磺代(DMSO)中的弱相互作用 - 第三纪酰胺溶液:DMSO作为溶剂的多功能性

Weak Interactions in Dimethyl Sulfoxide (DMSO) -- Tertiary Amide Solutions: the Versatility of DMSO as a Solvent

论文作者

Di Mino, Camilla, Clancy, Adam J., Sella, Andrea, Howard, Christopher A., Headen, Thomas F., Seel, Andrew G., Skipper, Neal T.

论文摘要

已通过广泛的氢/脱甲基甲基甲基甲基甲基二甲基氧化物(DMSO)(DMSO)研究了常见的极性质子溶剂(DMF)和二甲基乙酰氨酰胺(DMAC)(DMAC)的等摩尔混合物的结构。这些溶液的详细3维结构模型是通过经验潜在结构细化(EPSR)从中子数据得出的。分子间质量中心(COM)分布表明,酰胺的第一个配位外壳包括13-14个邻居,其中大约一半是DMSO。尽管存在接近理想的配位壳混合,但与纯液体相比,发现对酰胺酰胺结构的变化相对微妙。特定分子间原子 - 原子相关性的分析可以定量解释溶液中弱相互作用之间的竞争。我们发现甲基和甲基C-H至O氢键的层次结构形成了主要的局部基序,峰位置在2.5-3.0Å的范围内。我们还观察到各种各样的空间和分散相互作用,包括涉及酰胺pi-backbones的空间相互作用。对这些重要液体的结构景观的详细洞察证明了DMSO作为溶剂和中子衍射的无与伦比的分辨率的多功能性,这对于理解纳米级的弱分子间相互作用至关重要,从而将溶剂化的性质定制到特定应用中。

The structures of equimolar mixtures of the commonly used polar aprotic solvents dimethylformamide (DMF) and dimethylacetamide (DMAc) in dimethylsulfoxide (DMSO) have been investigated via neutron diffraction augmented by extensive hydrogen/deuterium isotopic substitution. Detailed 3-dimensional structural models of these solutions have been derived from the neutron data via Empirical Potential Structure Refinement (EPSR).The intermolecular Centre-of-Mass (CoM) distributions show that the first coordination shell of the amides comprises 13-14 neighbours, of which approximately half are DMSO. In spite of this near ideal coordination shell mixing, the changes to the amide-amide structure are found to be relatively subtle when compared to the pure liquids. Analysis of specific intermolecular atom-atom correlations allows quantitative interpretation of the competition between weak interactions in solution. We find a hierarchy of formic and methyl C-H to O hydrogen bonds form the dominant local motifs, with peak positions in the range 2.5-3.0 Å. We also observe a rich variety of steric and dispersion interactions, including those involving the amide pi-backbones. This detailed insight into the structural landscape of these important liquids demonstrates the versatility of DMSO as a solvent and the unparalleled resolution of neutron diffraction, which is critical for understanding weak intermolecular interactions at the nanoscale and thereby tailoring solvent properties to specific applications.

扫码加入交流群

加入微信交流群

微信交流群二维码

扫码加入学术交流群,获取更多资源